Laminating product including adhesion layer and laminate product including protective film

ABSTRACT

In a laminate product formed by an organic member and/or an inorganic member, high strength adhesion between the organic member and the inorganic member is achieved by providing an adhesion layer which includes amorphous carbon nitride (a-CNx:H) particularly between the organic member and the inorganic member. Further, in order to protect a laminate product formed by an organic member and/or an inorganic member, for example, an organic electronic element including an organic compound layer, such as an organic electroluminescence element, a protective film including at least amorphous carbon nitride and a protective layer having a laminate structure formed by sandwiching a vapor deposition inorganic film between plasma polymerized films are used. Thus, a protective film which is optimum to an organic electronic element, having high bending stress resistance, high shielding effect against moisture and oxygen existing in the air, and excellent resistance to high temperature and high humidity can be provided.

TECHNICAL FIELD

[0001] The present invention relates to an adhesion layer for improvingan adhesive property of a laminate product and a protective film forprotecting a laminate product.

BACKGROUND ART

[0002] Laminate structures which is composed of a plurality of thinfilms formed on a base member are employed in a variety of technicalfields. For example, a thin film is formed on a base member made of aninorganic or organic material, thereby forming an electronic device orprotecting a surface of the base member as a protective film.

[0003] In such a laminate structure, high adhesive strength of the thinfilm to the base member surface is often required so as to ensurereliability of the device, or for other reasons. Accordingly, in orderto enhance the adhesion, various methods have been proposed, such ascleaning the base member surface or improving the surface quality, andproviding an adhesion layer between the base member and the thin film.

[0004] Cleaning of the base member surface is commonly performed througha base member washing treatment employing an organic solvent, acid, oralkali, a UV ozone treatment, or a plasma treatment, as examples. Thesetreatments are usually performed as the thin film is formed on a glasssubstrate or an inorganic material substrate such as an Si substrate,and some of the washing methods improve the surface state, as describedin “Thin Film” by Sadafumi Yoshida (Baifukan, 1990).

[0005] With regard to improvement of surface quality of a base member, amethod has been provided for partially carbonizing a color filter or anorganic protective film which is formed covering the color film, so asto enhance adhesion between the color film and a transparent electrodemade of an ITO (Indium Tin Oxide) film which are formed on a glasssubstrate provided on one side of a liquid crystal panel, for example.Japanese Patent Laid-Open Publication No. Hei 10-319226 describes, forexample, formation of a carbonized layer between a color filter and atransparent electrode by exposing the color filter or an organicprotective film formed on the color filter to DC-plasma or RF-plasma fora short period of time or applying, before an adhesion layer is formed,ion irradiation to the color filter or the organic protective film whichhave been formed. The above publication describes that with such acarbonized layer, the protective function of the base layer is improvedand also adhesion of the base layer with respect to the adhesion layerand the transparent electrode, which are formed above the base layer,can be enhanced.

[0006] Formation of an adhesion layer between a base member and a thinfilm includes cases in which, for example, a hard coat layer is formedon a surface of plastic lens. Plastic lens is a soft material and musttherefore to be covered with a hard coat layer for surface protection.However, because adhesion between the plastic lens and the hard coatmaterial is low, in many cases, sufficient durability cannot be securedwhen a hard coat layer is formed directly on the lens surface. Toaddress this problem, Japanese Patent Laid-Open Publication No.2000-205305 proposes that a primer layer made of metal oxide particlesdispersed in a resin is coated and dried on the plastic lens surface andthen an adhesion layer is formed. It is reported that adhesion of a hardcoat layer to the plastic lens can be enhanced by thus forming a primerlayer on the plastic lens surface and then forming a hard coat layerthereon.

[0007] Further, in the field of a semiconductor devices or the like, itis required that a polymer resin having a relative dielectric constantlower than that of an inorganic film be used for an insulating film suchas an inter-layer insulating film. However, sufficient adhesion cannotbe secured between an insulating layer made of a polymer resin and metallines. In order to deal with this problem, Japanese Patent Laid-OpenPublication No. Hei 6-283615, for example, discloses that an adhesionlayer made of an amorphous fluorocarbon polymer with many dangling bondsis interposed between an insulating layer made of the above-describedpolymer resin and a metal layer (including a metal line).

[0008] In addition, recently, there has been an increasing demand for alighter and thinner electronic device which is formed on a plasticsubstrate used in place of a glass substrate. Because a plastic materialcannot provide high shielding property against foreign impurities (suchas water and oxygen) which an electronic device wishes to avoid, it isnecessary to form a barrier layer between the substrate and theelectronic device. However, adhesion between the plastic substrate andthe barrier layer remains low and requires further improvement. In thisregard, Japanese Patent Laid-Open Publication No. 2002-18994 proposesprovision of an adhesion layer made of Si or the like between theplastic layer and the barrier layer, and reports that adhesion betweenthe plastic substrate and the barrier layer is increased due to theprovision of the adhesion layer.

[0009] Improvement in the state of a substrate surface can be recognizedwhen a washing treatment using an organic solvent or acid and alkali,and an UV ozone treatment or a plasma treatment are employed withrespect to a substrate surface. However, organic base members such as aplastic substrate and a film substrate are often eroded by chemicalssuch as an organic solvent, acid, and alkali, and therefore cannot bewashed sufficiently to remove all foreign substances and contaminantsfrom the surface. Further, however the surface of the base member iscleaned, such cleaning will not improve the inherent adhesivenessbetween materials having a low chemical bonding power.

[0010] According to the plasma treatment of organic base members such asa plastic substrate and a film substrate, although the nature of thesurface can be modified, due to high plasma energy, a modified layer isformed through the layers to a region which is rather far from thesurface, and therefore the original property of the substrate is oftenlost. Moreover, when a plasma treatment is performed using a mixture ofdischarge gas and oxidizing gas such as oxygen so as to increasecleanness of the substrate, ashing is performed through the layers to adeep portion far from the substrate surface, and also evenness of thesubstrate surface is lost.

[0011] With a primer layer as described in the above Japanese PatentLaid-Open Publication No. 2000-206305, formation of a uniform andprecise thin film remains an industrially difficult task, and in manycases, the resulting film cannot maintain sufficient adhesive forceunder severe environment and is peeled off. Also, in optical element andlight emissive -element applications it is necessary that an adhesionlayer be optically transparent, which is difficult with either atransparent metal thin film or a Si film.

[0012] In addition, with the use of amorphous fluorocarbon polymerhaving many dangling bonds as an adhesion layer, adhesion between aninsulating layer made of a polymer resin and such an amorphousfluorocarbon polymer layer is enhanced, resulting in an increasedadhesion strength between the insulating layer and a metal layer.However, because fluorocarbon polymer, even in an amorphous state,includes substantially no elements which form strong chemical bondingbetween layers, it cannot maintain a sufficient adhesion force in a moresevere environment, with the result that metal layers are often peeledoff.

[0013] As described above, none of the above-described conventionalmethods are sufficient to improve adhesion between layers. Further, withthe variety of types of base members and thin film materials which areused today, there is a strong demand that high adhesion (a high level ofadhesive strength) be provided with respect to a variety of materialsand that adhesion between layers be maintained even in a severeenvironment.

[0014] Further, in a laminate structure in which one or more thin filmsmade of an inorganic or organic material are formed on a base membermade of an inorganic or organic material, a protective film which isformed so as to protect the laminated thin films from erosion bymoisture, oxygen and corrosive gas existing in the air and from mixtureof impurities or the like is required in a variety of technical fields.However, with the progress of diversification of base members anddevelopment of a device such as an organic electroluminescence elementincluding a mixture of an inorganic material layer and an organicmaterial layer, in addition to excellent shielding ability againstforeign materials or high strength, further functions are required forthese devices and the film itself which directly covers the base memberfor protection. For example, an ability to cover a device or a basemember, as the object of protection, with high adhesion and stabilityfor a long period whether or not the protection object is made of anorganic material or an inorganic material, and an ability to preventdamage to the protection object and significant stress generated withrespect to the protection object when forming the protective layer arerequired. However, while protective films preferably providing one ofthe two abilities has been proposed, no protective layers having thecombination of functions described above, especially those functionswhich require trade-off have yet been proposed.

[0015] In order to solve the above problems, the present invention hasan advantage of realizing an adhesion layer, a protective layer, or thelike, which can be applied to either an organic material or an inorganicmaterial.

DISCLOSURE OF THE INVENTION

[0016] In order to achieve the above objects, in accordance with oneaspect of the present invention, an organic/inorganic laminate structurehaving an organic member formed on an inorganic member comprises anadhesion layer at an interface between the inorganic member and theorganic member, and the adhesion layer includes amorphous carbonnitride.

[0017] In accordance with another aspect of the present invention, anorganic/inorganic laminate structure having an inorganic member formedon an organic member comprises an adhesion layer at an interface betweenthe organic member and the inorganic member, and the adhesion layerincludes amorphous carbon nitride.

[0018] When an organic member is formed on an inorganic member, or aninorganic member is formed on an organic member, in addition to theinternal stress contained in each material layer which is formed, astress caused by a difference of coefficient of expansion is furtherapplied to each layer, especially in a severe environment such as hightemperature and high humidity. In addition, because most combinations ofan inorganic member and an organic member provide a poor interfaceadhesion, there is a problem of peel-off and cracks. It is thereforenecessary to improve adhesion at the interface between the inorganicmember and the organic member.

[0019] In accordance with another aspect of the present invention, thereis provided a laminate product having an adhesive and a base member, atleast a surface of which has difficultly to adhere to the adhesive,wherein an adhesion layer is provided between the adhesive and the basemember and the adhesion layer includes amorphous carbon nitride.

[0020] The low adhesion between an inorganic material and an organicmaterial results from the facts that a chemical bonding force of thesematerials is weak and therefore the bonding force at the interfacedepends on the van der Waals force, and further that the van der Waalsforce acting on the interface by itself is not very large because anorganic material generally has a low density. In addition, poorwettablity between an organic material and an inorganic material isanother cause of such low adhesion.

[0021] Low adhesion between the base member and the adhesive alsoresults because the chemical bonding force of these materials is weak,and therefore the bonding force at the interface depends on the van derWaal forces, and further because the van der Waals force is relativelysmall when the adhesive has a low density.

[0022] Even when a combination of materials provides a weak force actingat the interface of these materials as described above, it is possibleto drastically increase the adhesion force by providing an adhesionlayer including amorphous carbon nitride (a-CNx:H) between thesematerials. An amorphous carbon nitride film includes carbon as its maincomponent, and therefore has excellent wettability and high adhesionwith respect to the organic material. Also, because of the high densityof the film, the amorphous carbon nitride film has high van der Waalsforces acting with respect to the inorganic material. In addition,because the chemical bonding force with respect to the inorganicmaterial is increased due to nitrogen atoms existing in the amorphouscarbon nitride film, adhesion between the amorphous carbon nitride filmand the inorganic member is increased.

[0023] Amorphous carbon nitride also exhibits high chemical bondingforce with respect to a base member which is otherwise difficult toadhere to due to the existence of nitrogen atoms, and can achieve highadhesion whether the base member having difficulty to adhere is made ofan inorganic material or an organic material. It is therefore possibleto increase adhesion between the base member having difficulty to adhereand the adhesive by forming an adhesion layer including amorphous carbonnitride between these members.

[0024] In accordance with another aspect of the present invention, theadhesion layer including amorphous carbon nitride can be formed by avapor deposition method using, as raw material, gas including one ormore of alkane, alkene, and alkyne, and gas including nitrogen andammonia.

[0025] Further, a plasma enhanced chemical vapor deposition method canbe adopted as the vapor deposition method. By using a plasma enhancedchemical vapor deposition method, the amorphous carbon nitride film canbe provided with a stronger chemical bonding and higher adhesion to thebase member or the adhesive due to the effect of radicals and ions.Moreover, a vapor deposition method can facilitate formation of a filmon a base member having a variety of shapes. Also, the method isapplicable in a room temperature and can therefore have a wide range ofapplications.

[0026] In accordance with a further aspect of the present invention, ina laminate product formed by either one or both of an inorganic memberand an organic member, an adhesion layer is provided between inorganicmembers or between inorganic members, or between the inorganic memberand the organic member, and the adhesion layer includes amorphous carbonnitride.

[0027] In addition to the combinations of an organic member formed on aninorganic member and an inorganic member formed on an organic member,when an inorganic member is formed on an inorganic member and when anorganic member is formed on an organic member, the adhesion at theinterface of these members is sometimes low. In such a case, accordingto the present invention, it is possible to maintain adhesion betweenlayers and prevent generation of peel-off, cracks or the like,especially under the severe environment of high temperature and highhumidity.

[0028] In accordance with anther aspect of the present invention, in alaminate product as above, the organic member includes one or more of asingle layer or a multi-layer thin film of an organic compound, a resin,and an adhesive.

[0029] In accordance with a further aspect of the present invention, ina laminate product as above, the organic member is an organic colorelement of a display element.

[0030] In accordance with a still further aspect of the presentinvention, in a laminate product as above, the organic color element isa color filter.

[0031] In accordance with a yet further aspect of the present invention,in a laminate product as above, the inorganic member is one or more ofoxide, nitride, carbide, metal and a semiconductor.

[0032] In accordance with another aspect of the present invention, asurface of a laminate base member in which inorganic members or organicmembers, or an inorganic member and an organic member, are layered, iscovered with a protective film, and the protective film includesamorphous carbon nitride.

[0033] With the provision of such a protective film, in any combinationof the films, namely, an organic member formed on an inorganic member,an inorganic member formed on an organic member, an inorganic memberformed on an inorganic member, and an organic member formed on anorganic member, these thin films of the laminate structure can becovered with high adhesion, and can therefore be protected from erosionby moisture, oxygen, and corrosive gas in the surrounding atmosphere,and from the mixing in of impurities or the like.

[0034] In accordance with another aspect of the present invention, anorganic electronic device comprises, on a base member, an organicelectronic element including at least an electrode and an organiccompound layer, and either one of or both a protective film which isformed covering the organic electronic element and a protective filmwhich is formed between the organic electronic element and the basemember, and the protective film includes amorphous carbon nitride.

[0035] In accordance with still another aspect of the present invention,in an organic electronic device as above, the protective film is asingle film made of the amorphous carbon nitride or a laminate filmformed by the amorphous carbon nitride an inorganic film.

[0036] In accordance with a further aspect of the present invention, inan organic electronic device as above, the film including amorphouscarbon nitride is formed by a vapor deposition method using, as a rawmaterial, gas including one or more of alkane, alkene, and alkyne, andgas including nitrogen and ammonia.

[0037] In a still further aspect of the present invention, in an organicelectronic device as above, the inorganic film includes one or more of anitride film, an oxide film, a carbon film, and a silicon film.

[0038] In yet a further aspect of the present invention, the inorganicfilm is one or more of a silicon nitride film, a boron nitride film, analuminum nitride film, a silicon oxide film, an aluminum oxide film, atitanium oxide film, an amorphous silicon film, an amorphous carbonfilm, and a diamond like carbon film.

[0039] In another aspect of the present invention, in an organic.electronic device as above, the protective film has a laminate structureformed by two or more layers including a film which includes theamorphous carbon nitride and the inorganic film, and the inorganic filmis formed between the amorphous carbon nitride film and the organicelectronic element.

[0040] As described above, durability of a device can be increaseddramatically when at least a film including amorphous carbon nitride isused as a protective film for an organic electronic device. Amorphouscarbon nitride has excellent flexibility and stress durability as anorganic protective film, and functions as a stress relaxation film ofthe element. On the other hand, amorphous carbon nitride has a densenesswhich is similar to that of the inorganic film, and therefore has a veryhigh shielding ability against moisture and oxygen. Further, because itis easy to control the stress characteristics of an amorphous carbonnitride film (a-CNx:H film) by controlling an amount of nitrogen (x)introduced into the film, a protective film having characteristics whichmeet application requirements can easily be formed.

[0041] Further, by providing a laminate structure formed by theamorphous silicon film and an inorganic film which uses a nitrogen film,an oxide film, a silicon film, a DLC film, or the like, it is possibleto even further improve shielding against moisture and oxygen.

[0042] Moreover, the protective film for the organic electronic deviceis useful not only as a protective film covering the element formed onthe substrate for externally protecting the element, but also, whenprovided between the substrate and the element, as a protective film forpreventing intrusion of moisture or the like into the element from thesubstrate side.

[0043] In accordance with another aspect of the present invention, in anorganic electronic device as above, the organic electronic element is anorganic electroluminescence element having at least one layer includingan organic compound between electrodes.

[0044] In accordance with still another aspect of the present invention,in an organic electronic device as above, the organic electronic elementincludes either an organic transistor or a liquid crystal element.

[0045] In accordance with a further aspect of the present invention, inan organic electronic device as above, the protective film includes theamorphous carbon nitride as a protective film having resistance to hightemperature and high humidity.

[0046] In accordance with another aspect of the present invention, thereis provided a manufacturing apparatus of an organic electroluminescenceelement including an element region having at least one organic compoundlayer between electrodes and a protective film covering at least theelement region, the protective film having a laminate structure formedby an amorphous carbon nitride film and an inorganic film and coveringthe element region. The apparatus comprises an element film formingchamber for forming each layer which constitutes the element region, aprotective film forming chamber for forming the amorphous carbon nitridefilm, and an inorganic film forming chamber for forming the inorganicfilm, and at least each protective film forming for forming theamorphous carbon nitride film or the inorganic film which is previouslyformed covering the element region, and the element film forming chamberare connected directly or via a transportation vacuum chamber.

[0047] With the above structure, it is possible to transport a substrateon which an organic EL element has been formed, to a protective filmforming device without exposing the substrate to the atmosphere. Byenabling transportation of the organic EL element to the protective filmforming device without being exposed to the atmosphere, each layer canbe laminated in-situ.

[0048] In accordance with another aspect of the present invention, anorganic electronic device comprises, on a base member, an organicelectronic element including at least an electrode and an organiccompound layer, and either one of or both a protective film formedcovering the organic electronic element and a protective film formedbetween the organic electronic element and the base member, and theprotective film includes a lamination film in which a vapor depositioninorganic film and a plasma polymerized film which is formed using amaterial including at least one type of an organic compound arealternately layered and in which the vapor deposition inorganic film issandwiched by the plasma polymerized films.

[0049] In the above organic electronic device, the plasma polymerizedfilm can be formed by including any of amorphous carbon nitride,amorphous carbon, hetero five-membered ring organic compound polymer,fluorine organic compound polymer, chlorine organic compound polymer,acrylic organic compound polymer, and silicon organic compound polymer,for example. The vapor deposition inorganic film can be formed byincluding any of silicon nitride, boron nitride, aluminum nitride,silicon oxide, aluminum oxide, titanium oxide, amorphous silicon, anddiamond like carbon, for example.

[0050] By adopting a multi-layer lamination film, formed by a plasmapolymerized film including an organic compound and a vapor depositioninorganic film, as a protective film for an organic electronic element,the following advantages can be obtained. Specifically, the bendingstress resistance is increased by forming a vapor deposition inorganicfilm which has high moisture proof property but has low bending stressresistance to have a small thickness and the moisture proof propertywhich deteriorates accordingly can be compensated for by using amulti-layer structure formed with a plasma polymerized film including anorganic compound with excellent stress relaxation and high bendingstress resistance. Thus, in an organic electronic device of the presentinvention, it is possible to realize high bending stress resistance andhigh moisture proof property due to a protective film formed bymulti-layer lamination layers.

[0051] Further, because the protective film of the present invention isformed by sandwiching the vapor deposition inorganic film between theplasma polymerized films, the plasma polymerized films provided aboveand below the vapor deposition inorganic film can reliably preventstress concentration on the vapor deposition inorganic film. When aplasma polymerized film is provided only on one surface of the vapordeposition inorganic film, when these films are bent, stress isgenerated due to a characteristic difference between these films andstress concentration is generated in a step portion or a projectingportion. In particular, when stress concentration is caused in aninorganic film which has low bending stress resistance as describedabove, cracks are generated in the film, or peeling-off occurs at thefilm interface and moisture proof property is reduced. By providingplasma polymerized films having the same or similar characteristicssandwiching the vapor deposition inorganic film, the plasma polymerizedfilms will provide an opposing effect with respect to the vapordeposition inorganic film interposed between them, reducing thelikelihood of stress generation, providing a balancing effect, andthereby preventing stress concentration. Consequently, even when thebase member is bent, generation of cracks or reduction in moistureproofing property can be prevented.

[0052] Also, when only one plasma polymerized film including an organiccompound and only one vapor deposition inorganic film are laminated,thermal stress is generated due to a difference in thermal expansioncoefficient between these films, resulting in warping of the protectivefilm and stress concentration in a step portion or the like, wheremoisture resistance ability will easily be affected. However, byadopting, in a protective film, a laminate structure formed bysandwiching a vapor deposition inorganic film between plasma polymerizedfilms as in the present invention, the thermal stress between the plasmapolymerized film and the vapor deposition inorganic film can be balancedvia the vapor deposition inorganic film. Accordingly, the protectivefilm will not warp or bend, and cracks can be prevented. Further,deterioration of moisture resistance property in the protective film dueto thermal stress can be prevented, and sufficient extension of life canalso be achieved for an organic electronic element which is exposed tohigh temperature and high humidity conditions.

[0053] In addition, because the plasma polymerized film including anorganic compound functions as a stress relaxation layer, the thermalstress between the plasma polymerized film and the vapor depositioninorganic film, between the plasma polymerized film and the organicelectronic element, and between the plasma polymerized film and thesubstrate, can be relaxed by the plasma polymerized film, and the effectof thermal stress on the inorganic film or the element can be reduced,so that deterioration of element characteristics and reduction inmoisture proofing property can both be prevented.

[0054] A protective film having a multi-layer laminate structureaccording to the present invention has both a high bending stressresistance and a superior moisture proofing property. Accordingly, evenwhen an organic electronic element is formed on a substrate using aflexible material, increased reliability and extended service life canbe achieved by covering the organic electronic element with a protectivefilm as described above. Further, by forming the protective film of thepresent invention between the organic electronic element and thesubstrate, significant reduction in moisture resistance property due togeneration of cracks at the time of bending the substrate or thermalstress is unlikely. It is therefore possible to reliably preventintrusion of moisture and oxygen into the element from the substrateside.

[0055] Further, the protective film of the present invention covers theorganic electronic element and is also formed between the substrate andthe element region. It is therefore possible to prevent intrusion ofexternal moisture and oxygen including those from the substrate, therebymore reliably protecting the organic electronic element.

[0056] In accordance with another aspect of the present invention, thethickness of each vapor deposition inorganic film layer in thelamination layer is 0.5 μm or less. Because the protective film of thepresent invention has a multi-layer laminate structure formed by aplasma polymerized film and a vapor deposition inorganic film, theprotective film need not have a thickness of 0.5 μm or more, acharacteristic which is necessary for covering the steps of the organicelectronic film only with an inorganic film. Because an inorganic filmhas large a Young's modulus and large internal stress, cracks are easilygenerated when the film is bent or otherwise deformed, and such aninfluence is further increased when the inorganic film has a largethickness, as described above. By forming the inorganic film to have athickness of 0.5 μm or less, however, the functionality of theprotective film would not be deteriorated, and high bending stressresistance can be achieved while high moisture proof ability ismaintained.

[0057] In a further aspect of the present invention, in the aboveorganic electronic device, the number of layers in the lamination filmis 50 or less.

[0058] In a still further aspect of the present invention, in the aboveorganic electronic device, the total thickness of the lamination filmequals to or greater than the total thickness of the organic electronicelement, and is 10 μm or less.

[0059] Because both the plasma polymerized film and the vapor depositioninorganic film of the present invention are formed using a vapordeposition method, the films both demonstrate superior covering propertywith respect to the steps, in contrast to films formed by an evaporationmethod or the like. Also, because the protective film is formed by alamination film, making the total thickness of the protective film equalto or greater than the total thickness of the organic electronicelement, so that sufficient step covering can be achieved, is a simpleprocess. Because a protective film having a thickness which isunnecessarily large is disadvantageous in view of manufacturing cost andbecause a total thickness of no more than 10 μm would be sufficient forthe protective film, a maximum of 50 would be sufficient as the totalnumber of laminated film layers in the protective film.

[0060] Further, an organic electronic element according to the presentinvention is applicable as an organic electroluminescence element, anorganic transistor, and an element including a liquid crystal element,for example.

BRIEF DESCRIPTION OF THE DRAWINGS

[0061] These and other objects of the invention will be explained in thedescription below, in connection with the accompanying drawings, inwhich:

[0062]FIG. 1 is a view showing a structure of a laminate productaccording to a first embodiment of the present invention.

[0063]FIG. 2A is a view showing an application example of the laminateproduct structure according to a sixth example of the present invention.

[0064]FIG. 2B is a view showing another application example of thelaminate product structure according to the sixth example of the presentinvention.

[0065]FIG. 3 is a view showing an application example of the protectivefilm according to a second embodiment of the present invention.

[0066]FIG. 4 is a view showing another application example of theprotective film according to the second embodiment of the presentinvention.

[0067]FIG. 5 is a schematic cross sectional view showing a structure ofthe organic EL element according to the second embodiment and an eighthexample of the present invention.

[0068]FIG. 6 is a schematic cross sectional view showing a structure ofthe organic EL element according to the second embodiment and a ninthexample of the present invention.

[0069]FIG. 7 is a schematic cross sectional view showing a structure ofthe organic EL element according to the second embodiment and a tenthexample of the present invention.

[0070]FIG. 8 is a schematic cross sectional view showing a structure ofthe organic EL element according to the second embodiment and aneleventh example of the present invention.

[0071]FIG. 9 is a schematic cross sectional view showing a structure ofthe organic EL element according to the second embodiment and a twelfthexample of the present invention.

[0072]FIG. 10 is a view showing one example of an organic EL elementmanufacturing apparatus according to the present invention.

[0073]FIG. 11 is a schematic cross sectional view showing a structure ofthe organic electronic device according to the fourth embodiment athirteenth example of the present invention.

[0074]FIG. 12 is a schematic cross sectional view showing a structure ofthe organic EL element according to the fourth embodiment and thirteenthto seventeenth examples of the present invention.

DETAILED EXPLANATION OF PREFERRED EMBODIMENTS

[0075] Preferred embodiments of the present invention will be describedwith reference to the drawings.

Embodiment 1

[0076] According to a first embodiment of the present invention, asshown in FIG. 1a laminate product comprises an adhesion layer 20including amorphous carbon nitride (a-CNx:H where x is an arbitrarynumber) at an interface of a laminate structure formed by an inorganicmember 10 and an organic member 30. As described above, an amorphouscarbon nitride film includes carbon as its main component, and thereforehas excellent wettability and high adhesion with respect to organicmaterial. Also, because high Van der Waals force acts between theadhesion layer and the inorganic material due to the high density of theadhesion layer, high adhesion can also be obtained between the adhesionlayer and the inorganic layer. Further, because the adhesion layer is adense layer with excellent surface covering property, its adhesion forcecan further be improved.

[0077] The inorganic member and the organic member may have a basemember in any state, such as a thin film, a thick film, or a substratehaving a desired shape. The laminate structure can be realized either byforming an organic member on an inorganic member, or by forming aninorganic member on an organic member. With the provision of theadhesion layer of the present embodiment, which is a film includingamorphous carbon nitride, between the inorganic member and the organicmember, it is possible to improve adhesion between the inorganic memberand the organic member. Moreover, regardless of whether or not the basemember is an inorganic member or an organic member, by forming anadhesion layer including amorphous carbon nitride between an adhesiveand a base member, at least the surface of which exhibits a difficultyfor adhering to the adhesive agent, adhesive force between the basemember and the adhesive can be improved.

[0078] The inorganic member may include oxide, nitride, carbide, metal,semiconductor, or the like, and may be, for example, a glass substrate,a silicon oxide film, and a metal oxide film. It should be noted thatalthough pure metals provide somewhat low adhesion to the adhesion layerof the present invention formed of amorphous carbon nitride, otherinorganic materials can provide very high adhesion force.

[0079] The organic member may be a resin such as an acrylic resin, esterresin, carbonate resin, fluorocarbon resin, chlorine resin, epoxy resin,silicon compound resin, amide resin, imido resin, phenolic resin,melanin resin, ethylene resin, and propylene resin, an organic thin filmsuch as a plasma polymeric film of an organic compound, and an adhesivesuch as epoxy adhesive, ultraviolet curing adhesive, and thermosettingadhesive.

[0080] In the first embodiment, the laminate structure can be appliedeither to a laminate structure in which a material film and an adhesiveare layered on a base member (substrate) having a flat surface, a curvedsurface or any shape in accordance with its usage, or to a laminatestructure formed by a plurality of material films.

[0081] The adhesion layer including amorphous carbon nitride can beformed by a vapor deposition method using, as a raw material, gasincluding at least one or more of alkane, alkene, and alkyne, and gasincluding nitrogen or ammonia, and can be formed by plasma enhancedchemical vapor deposition using methane gas and nitrogen gas as rawmaterials. The thickness of the adhesion layer is not particularlylimited, and may be approximately between 50 nm to 300 nm, for example.When the adhesion layer is too thin, it becomes non-uniform or has low-covering property. Even when the adhesion layer is thicker thannecessary, on the other hand, adhesion is not increased accordingly, andtherefore the adhesion layer should preferably have an appropriatethickness. Further, a plasma polymerized film made of amorphous carbonnitride is colored, though slightly, when it has a thickness ofapproximately 300 nm or more. Therefore, it is preferable to use aplasma polymerized film having such a thickness as an adhesion layer foran optical element and to use a plasma polymeric film havingapproximately 300 nm or less when a transparency is required for thefilm.

Embodiment 2

[0082] A second embodiment will be described. While amorphous carbonnitride (a-CNx:H) is used for an adhesion layer in the above firstembodiment, in the second embodiment of the present invention, amorphouscarbon nitride including hydrogen is used as a protective film. Morespecifically, a protective film covering a surface of a laminate basemember in which inorganic members, organic members, or inorganic andorganic member are lamimated, includes amorphous carbon nitride.

[0083] In any combination of films, namely, an organic member formed onan inorganic member, an inorganic member formed on an organic member, aninorganic member formed on an inorganic member, and an organic memberformed on an organic member, when such a protective film is provided,the thin films of the laminate structure can be covered with highadhesion, and can therefore be protected from erosion by moisture,oxygen, and corrosive gas existing in the air and from mixture ofimpurities or the like.

[0084] Organic electronic devices using an organic compound as afunctional material, such as organic electroluminescence elements(hereinafter referred to as “organic EL elements”), for example, havebeen noted and studied. Because an organic compound has a higher degreeof freedom for molecular design in accordance with the function comparedto an inorganic compound, light emissive elements emitting variouscolors can be realized by an organic electronic element using such anorganic compound, and realization of a transistor with high mobilitywhich can be formed at a low temperature can be expected.

[0085] In such an organic electronic element using an organic compound,it is known that an organic compound layer is vulnerable to erosion bymoisture and oxygen in the air. For example, an organic EL element,under the existence of moistures and oxygen, suffers from deteriorationsuch as generation of dark spots and short-circuit of the element.Accordingly, in order to prevent such deterioration and protect theorganic EL element, a method has been employed for sealing the wholeelement with a cover glass, a can package, or the like, in an atmosphereof dry nitrogen, argon gas, or the like.

[0086] Further, in order to enlarge an element panel in a simple mannerwith a low cost, a method of covering the entire organic EL element witha protective film has been proposed. Use of amorphous carbon (JapanesePatent Laid Open Publications No. Sho 63-259994 and No. Hei 7-161474), asilicon nitride film and silicon oxide film (Japanese Patent Laid OpenPublication No. Hei 4-73886), and DLC (Diamond Like Carbon) (JapanesePatent Laid Open Publication No. Hei 5-101885), as well as amorphoussilica (Japanese Patent Laid Open Publication No. Hei 5-335080),SiZnO.SiZnON (Japanese Patent Laid Open Publication No. Hei 8-96955) asa protective film, and use of polyparaxylene (Japanese Patent Laid OpenPublication No. Hei 4-137483), polyurea (Japanese Patent Laid OpenPublication No. Hei 8-222368), or the like, as an organic material, hasbeen proposed.

[0087] A structure in which a plurality of protective layers arelaminated has also been proposed. For example, a laminate structurecomposed of a layer which is formed by vapor deposition and a layer madeof a photosetting resin (Japanese Patent Laid Open Publication No. Hei4-267097) and a laminate structure composed of an inorganic protectivefilm and a sealing resin (Japanese Patent Laid Open Publication No. Hei11-40345) are reported.

[0088] Further, a structure in which an organic protective film and aninorganic oxygen absorbing film or an inorganic protective film arelaminated is disclosed in Japanese Patent Laid Open Publications Nos.Hei 7-169567, Hei 7-192868, 2000-068050, and 2001-307873, for example.

[0089] In addition, use of “Barix” as a protective film for a substratewhich is a flexible substrate is reported (DISPLAYS 22, 65 (2001)).

[0090] Installation of display devices which use the above-describedorganic EL element, for example, in various devices has been studied. Inorder to employ such a display device as a display device mounted in avehicle (in-vehicle display), it is necessary that the device beadaptable to high temperature and high humidity conditions. Shielding ofan organic EL element from moisture and oxygen using the protective filmas described above is regarded as an essential technique for providing athin and large organic EL display device at a low cost. In thein-vehicle application described above, however, it is necessary toreliably prevent the formation of cracks in a protective film andpeeling-off of the protective film caused by thermal stress andhygroscopic stress under high temperature and high humidity. In order toavoid these phenomena, it is necessary that the protective film be athin film having excellent stress durability and high adhesion forcewith respect to the organic EL element.

[0091] Also, there is a strong demand for increased resistance to hightemperature and high humidity, not only in organic EL elements, but alsoin other organic electronic devices such as liquid crystal displaydevices and organic transistors or the like. Accordingly, it is requiredthat a protective film be a thin film with excellent stress durabilityand high adhesion force with respect to an organic electronic device.

[0092] Further, when a flexible substrate formed by a plastic member isadopted as a base member for forming an element so as to realize anorganic electronic device having flexibility for reducing weight andthickness or the like, sealing of the element using a cover glass and acan package is not possible, and it is therefore necessary to blockmoisture and oxygen using a protective film. Because a protective filmof an organic electronic element which is formed on such a flexiblesubstrate must have a stable property with respect to bending, such aprotective film must have excellent bending stress durability and highstress relaxation property.

[0093] Heretofore, however, there did not exist a protective film whichsatisfied the above requirements.

[0094] Also, although inorganic protective films such as a siliconnitride film and a silicon oxide film, which are often used as aprotective film in the semiconductor field, have high shielding propertyagainst moisture and oxygen in the air and high thermal conductivity,they have disadvantages that thermal stress is large due to a largeYoung's modulus and that they are made of a relatively fragile materialand are therefore vulnerable to cracking. In particular, when such aninorganic protective film is used as a protective film for an organic ELelement, it is necessary to set the thickness of the inorganicprotective film to approximately 1 μm, at least greater than 0.5 μm, inorder to increase moisture proof property. Such a thick inorganicprotective film, however, suffers from problems that influence of stresson the film is actually increased, and that, under high temperature andhigh humidity conditions, not only the film is subjected to cracks, butalso sufficient durability with respect to bending which is necessarycannot be obtained.

[0095] Organic protective films such as polyparaxylene and polyureadescribed above have excellent flexibility and can therefore providehigh stress durability when they are adopted in an organic electronicelement which is formed on a flexible substrate. However, because thesefilms have low density and low shielding property against moisture andoxygen, they are not suitable as a protective film for an organicelectronic element for in-vehicle use, for example.

[0096] A protective film formed by an amorphous carbon (a-C) film cannotbe used for an element which is formed on a flexible substrate becauseof inherent problems such as, for example, that the film has pooradhesion to an organic electronic element, the stress on the film itselfis difficult to control, and cracking and peeling-off results under hightemperature and high humidity conditions.

[0097] In a case where an organic electronic element is covered with acombination of an inorganic protective film and a sealing resin, themoisture resistance property is insufficient when the thickness of theinorganic protective film is reduced, whereas the stress durability islowered when the thickness of the inorganic protective film isincreased. Because such a “trade-off” relationship exists between thecharacteristics, enhancement of moisture resistance property andenhancement of stress durability are incompatible.

[0098] Further, even in the above-described structure in which anorganic protective film and an inorganic protective film are laminatedas described in Japanese Patent Laid-Open Publication No. Hei 7-169567,because the above problems concerning each of an inorganic protectivefilm and an organic protective film remain unsolved, the protectingfunction which is required cannot be offered when such a structure issimply adopted as a protective film for an organic electronic elementusing a flexible substrate.

[0099] Application of a protective film which uses “Barix” to a flexiblesubstrate is reported, as described above. The protective film using“Barix” is formed by evaporation. However, an organic film formed byevaporation has low adhesion to an inorganic film, and has poordurability under high temperature and high humidity environment. Also,the covering property of such a film is inferior.

[0100] The protective film according to the second embodiment of thepresent invention differs from the conventional protective filmsdescribed above, and can cover a laminate product formed by an organicmember and an inorganic member with high adhesion. Further, theprotective film of the second embodiment can suppress stress whichcauses cracking in a laminate product when forming the film and stresswhich is generated at an interface after film formation, and can alsoimprove resistance to moisture.

[0101] In the second embodiment, as shown in FIG. 3, a laminate productcomprises a protective film 40 including amorphous carbon nitride(a-CNx:H where x is an arbitrary number) so as to cover a laminatestructure formed by an inorganic member 10 and/or an organic member 30.Alternatively, as shown in FIG. 4, a protective film 40 may also beprovided in a laminate structure formed by an inorganic member 10 and/oran organic member 30, so that one inorganic member 10 and/or organicmember 30 can be protected from erosion by moisture, oxygen, andcorrosive gas and mixture of impurities from the other inorganic member10 and/or organic member 30.

[0102]FIG. 5 schematically shows a sectional structure of an organicelectronic device according to the present invention, and FIG. 6schematically shows a structure of an organic EL element which is usedas an organic electronic element in FIG. 5. In the followingdescription, an organic EL element will be mainly described as anexample of an organic electronic element. A flexible material can beused as a material for a substrate 11, and various plastic materialsincluding polyethylene terephthalete (PET), ester resin, acrylic resin,fluorocarbon resin can be used. Although it is necessary to use anoptically transparent material for the substrate 11 when the organic ELelement is configured to emit light through the substrate, an opticallyopaque material may be used when light is emitted from the element side.On the substrate 11, a first electrode 13, an organic compound layer 31,and a second electrode 15 are laminated to constitute an element region.The organic compound layer 31 includes at least an organic emissivematerial. Electrons and holes are injected from the first electrode 13and the second electrode 15 into the organic compound layer, where theelectrons and the holes are recombined to excite the organic emissivematerial, thereby emitting light. The substrate 11 may be formed by atransparent glass or plastic substrate. The materials used for thelayers of the organic EL element formed on the substrate 11 are notparticularly limited, and, for example, in addition to the materialswhich are conventionally proposed as materials for an organic ELelement, new materials which will be developed in the future and anycombination such new materials can also be used. As an example, thefirst electrode 13 functions as a hole injection electrode (anode) andis formed using a transparent electrode such as ITO (Indium Tin Oxide),and the second electrode 15 functions as an electron injection electrode(cathode) and may also have a laminate structure including an electroninjecting layer 14 made of lithium fluoride (LiF) as shown in FIG. 6, inaddition to a single-layer structure of a metal electrode such as Al.The organic compound layer 31 is configured to include at least anorganic emissive material as described above, and may have either asingle layer structure of an emissive layer, a two-layer structureincluding hole transport layer/emissive layer or emissive layer/electrontransport layer, or the like, a three-layer structure including holetransport layer/emissive layer/electron transport layer, or amulti-layer structure further including a charge (hole, electron)injection layer, depending on the characteristics of an organic materialor the like which is used. For example, as shown in FIG. 6, the organiccompound layer 31 can be formed by, from the first electrode 13 side, ahole injection layer 32 made of copper phthalo cyanine (CuPc) or thelike, a hole transport layer 33 made of triphenyl amine tetramer (TPTE)or the like, and an emissive layer 36 made of quinolinol aluminumcomplex (Alq₃), and can emit green light which originates from Alq₃. Inthe example shown in FIG. 5, a hole injection layer 32, a hole transportlayer 33, and a hole transport layer 34 are sequentially laminated, inthat order, between the first transparent electrode 13 and the secondmetal electrode 15. In FIG. 5, the second metal electrode 15 actuallyforms a laminate structure together with an electron injection layer 14made of lithium fluoride which is formed on the surface of the secondelectrode 15 facing the hole transport layer 34.

[0103] In the second embodiment, the protective film 40 is formedcovering the organic EL element having the above structure. As shown inFIG. 5, the protective film 40 is formed, after formation of the secondelectrode 15 which is the uppermost layer of the element, so as to coverthe entire region of the element on the substrate 11, and protects theorganic EL element from moisture and oxygen in the air. Amorphous carbonnitride (a-CNx:H) described above is used as a material for theprotective film 40. An a-CNx:H film has a density similar to that of aninorganic film and therefore has high shielding property againstmoisture and oxygen in the air. Further, an a-CNx:H film has excellentcovering property and evenness, and also has high stress durabilitybecause it has flexibility as an organic film and can reduce thermalstress and hygroscopic stress. In addition, because an element Ncontained in the a-CNx:H film increases bonding force to the basemember, the a-CNx:H film can be realized as a film with low stress.Therefore, even when an a-CNx:H film is provided as a protective filmfor an organic EL element under high temperature and high humidityconditions, it is possible to prevent cracking and peeling-off. Further,the a-CNx:H film can be formed by-plasma enhanced chemical vapordeposition using methane gas and nitrogen gas as raw materials, and isvery advantageous in reducing a manufacturing cost of an organic ELelement because methane gas and nitrogen gas which are raw materials areinexpensive and also a film forming device (plasma vapor depositiondevice) is also relatively inexpensive. Also, by controlling the ratioof the methane gas and the nitrogen gas which are raw materials, it ispossible to adjust the ratio(x) of N in the film, so that thecharacteristics, particularly the stress or the like, of the a-CNx:Hfilm which is formed in accordance with the N ratio can be controlledaccurately. Accordingly, such an a-CNx:H film is very excellent as aprotective film for an organic EL element.

[0104] The protective film 40 is not limited to a single layer structureincluding an a-CNx:H film as described above and shown in FIG. 5, andmay alternatively be employed to form a laminate structure with otherprotective material film. When the protective film 40 forms a laminatestructure with, for example, an inorganic protective film having highshielding property against moisture and oxygen, further improvement ofthe shielding property against moisture and oxygen and the stressrelaxation ability become compatible, and adhesion to the organic ELelement can be enhanced. Preferably, the inorganic protective film foruse in combination with an a-CNx:H film is made thin, because the stressis increased when such an inorganic protective film is thick. A nitridefilm, an oxide film, a carbon film, or a silicon film can be used as aninorganic protective film. More specifically, a silicon nitride film(SiN film), a boron nitride film, an aluminum nitride film, a siliconoxide film (SiO₂ film), an aluminum oxide film (Al₂O₃ film), a titaniumoxide film (TiO₂ film, TiCO film or the like), an amorphous siliconfilm, an amorphous carbon film, or a diamond like carbon (DLC) film canbe used.

[0105] As shown in FIG. 6, the protective film 40 can have anotherstructure in which an a-CNx:H film 41 and a SiN film 43 are sequentiallyformed from the organic EL element side. By laminating the SiN film,which is a very dense film, on the a-CNx:H film, the ability of theprotective film 40 to shield intrusion of moisture and oxygen from abovethe element can be enhanced. At the same time, adhesion between the SiNfilm 43 and the second electrode 15 can be enhanced, thereby improvingreliability of the organic EL element.

[0106] Further, as shown in FIG. 7, the protective film 40 may adopt alaminate structure in which an inorganic protective film and an a-CNx:Hfilm are laminated in the reversed manner. More specifically, theprotective film 40 can be formed in the laminate structure in which aSiN film 43 and an a-CNx:H film 41 are sequentially formed in this orderfrom the organic EL element side. Because the film structure of thea-CNx:H film is dependent on the underlying layer, when a dense filmsuch as the SiN film 43 is used as the underlying film, the a-CNx:H film41 which is formed thereon can be dense and have high shielding functionagainst moisture and oxygen.

[0107] Moreover, a SiN film has high absorptivity with respect to thebase member surface because silane, which is a raw material of the film,is chemically active. On the other hand, alkane gas, alkene gas, or thelike of methane gas which is a raw material of the a-CNx:H film is notso active as silane. Accordingly, the a-CNx:H film has lower adhesion tothe second electrode (metal electrode ) 15 of the organic EL elementthan the SiN film. Consequently, by forming the SiN film below thea-CNx:H film, it is possible to cover the organic EL element with theSiN film with high adhesion and to form an a-CNx:H film having asuperior quality on the SiN film, so that the resistance to hightemperature and high humidity can be further increased. Also, there maybe cases where particles of dust and waste are attached to the surfaceof the organic EL element at the time of forming the protective film.The SiN film 43 can be formed on such a particle surface with highadhesion in a manner similar to when it is formed on the organic ELelement surface. By covering the SiN film 43 with the a-CNx:H film 41,even the region to which such particles are attached can be easilycovered with the a-CNx:H film 41 having high evenness and high coveringproperty. It is therefore possible to solve a problem of poor coveringproperty of the protective film at these particle regions which allowsintrusion of moisture and oxygen into the organic EL element through thediscontinuous portions of the protective film.

[0108] Further, in the protective film 40, an additional film havinghigh shielding ability against moisture and oxygen, such as an inorganicprotective film including a SiN film, for example, may further be formedabove the a-CNx:H film shown in FIG. 7. FIG. 8 shows a protective film40 having such a three-layere structure in which a SiN film 43, ana-CNx:H film 41, and a SiN film 43 are sequentially laminated in thisorder from the organic EL element side. Because the SiN film 43 isformed as the uppermost layer of the protective film, it is possible toprevent moisture or the like from entering from above the organic ELelement more reliably. As in the case of the above-described examplestructure, it is preferable that this uppermost SiN film 43 is formed asa thin film in a range where the film has a shielding effect againstmoisture or the like and has a required strength, so as not to increasethe stress in the film.

[0109] Alternatively, the protective film 40 may also be formed in amulti-layer structure in which more a-CNx:H films and more SiN films arelaminated. This results in further increased reliability of theprotective film.

Embodiment 3

[0110] A third embodiment of the present invention will be described.FIG. 9 shows a schematic sectional structure of an organic EL element ofthe third embodiment. The third embodiment differs from the secondembodiment in that, in the third embodiment, in addition to theprotective film 40 which covers the organic EL element on the secondelectrode 15 side, the protective film (buffer layer) 49 is furtherformed between the substrate 12 and the organic EL element (the firstelectrode 13 in this example). When a substrate which has superiorflexibility and is yet more inexpensive than a glass substrate, forexample, a plastic substrate, is used as the substrate 12 for formingthe element, it is necessary to prevent intrusion of moisture and oxygenfrom the substrate side because the plastic substrate has lowershielding property than that of the glass substrate. By forming theprotective film 49 between the substrate 12 and the organic EL elementas shown in FIG. 9, the organic EL element can be protected morereliably. The protective film 40 which covers the organic EL element mayadopt a single layer structure including an a-CNx:H film and amulti-layer structure further including a SiN film or the like asdescribed in the second embodiment.

[0111] It is preferable, both in respect to stress relaxation andmoisture and oxygen shielding, that the protective film 49 is alsoformed by an a-CNx:H film. In this regard, the protective film 40 is notlimited to a single layer structure of an a-CNx:H film, and morepreferably has a laminate structure formed with a thin inorganicprotective film such as a SiN film. As a laminate structure, a structurein which an a-CNx:H film and a SiN film are sequentially formed in thisorder from the substrate 12 side, a structure in which a SiN film and ana-CNx:H film are sequentially formed in this order from the substrate 12side, or a multi-layer structure of these layers, for example, can beadopted.

[0112] It is possible to form an organic EL element, which is coveredwith a protective film as described in the above second and thirdembodiments, by using a manufacturing apparatus shown in FIG. 10. In themanufacturing apparatus of FIG. 10, all the film forming chambersincluding element film forming chambers (an organic compound layerforming changer 102, a second electrode forming chamber 103), eachforming each layer of an organic EL element having an organic layerbetween electrodes and film forming chambers for protective film to beformed on the element forming region (an inorganic protective filmforming chamber 201, an a-CNxH forming chamber 202), are coupled to acommon transportation vacuum apparatus 300 via the respective gatevalves (GV), such that the whole apparatus has a cluster structure. Asubstrate introducing chamber and a substrate extracting chamber can beconfigured as a common chamber 100.

[0113] Such a cluster structure increases tolerance of the manufacturingapparatus for changing formation processes. For example, when it isdesired to change the order of laminating films described in FIG. 6 tothe reverse order shown in FIG. 7, or increase the number of laminatefilms in the protective film 40 as shown in FIG. 8, for example, theapparatus can easily deal with such changes. Further, the area requiredfor setting the apparatus can be reduced easily. Of course, a so-calledinline structure in which the element film forming chambers and filmforming chambers for protective film are directly connected can also beadopted. Between the chambers, a gate valve is provided so as to makeeach chamber independent from each other chamber. With any of the aboveapparatus structures, it is possible to cover the element region withthe protective film 40 without exposing the organic EL element to theambient air after forming the organic compound layer which constitutesthe organic EL element, so that the organic compound layer of the ELelement which easily deteriorates when exposed to atmosphere can bereliably protected.

[0114] As described above, an a-CNx:H film forming a protective film canbe formed using plasma enhanced chemical vapor deposition. Further, aninorganic protective film which forms a multi-layer structure togetherwith the a-CNx:H film, such as a SiN film, for example, is preferablyformed by a plasma CVD method. Of course, an inorganic protective filmsuch as a SiN film and an SiO₂ film can be formed using a sputteringmethod which is used in a semiconductor device or the like. However, anorganic El element which is more vulnerable to damages than asemiconductor device or the like is significantly damaged by sputtering.In addition, although the main role of a protective film is to shieldthe element from the ambient air, the density and coverage of theprotective film obtained by sputtering is inferior to that obtained byplasma CVD. For these reasons, it is more preferable to form theinorganic protective film using a plasma CVD method. In particular, whena SiN film is formed on the organic EL element side as shown in FIGS. 7and 8, the plasma CVD method is desired so as to prevent damage of theorganic EL element.

[0115] In the above examples, it has been descried that the organic ELelement is an object of protection by the protective film. However, theprotective film using an amorphous carbon nitride material describedabove according to the embodiments of the present invention cansimilarly achieve a substantial effect, when it is used for protectingother elements whose functional material needs to be protected frommoisture and oxygen in an organic electronic device, such as so-calledorganic transistor which uses an organic material as a material of theactive layer.

Embodiment 4

[0116] A fourth embodiment of the present invention will be describedwith reference to FIGS. 11 and 12. According to the fourth embodiment,as a protective film for protecting an organic electronic element (anorganic EL element, for example) 310 as described in the above secondand third embodiments, a laminate film formed by laminating a plasmapolymerized film 47 and a vapor deposition inorganic film 48 alternatelyto form a film of at least three layers including the plasma polymerizedfilm 47 interposed between the chemical vapor deposition films 48 isused.

[0117] In the fourth embodiment, a protective film having such amulti-layer laminate structure is used both as a first protective film45 formed between the substrate 12 and an organic EL element and as asecond protective film 46 formed covering the organic EL element.However, a similar effect can be obtained when such a structure is usedfor only one of the first and second protective films 45, 46.

[0118] By adopting a protective film having the above-described laminatestructure as the second protective film 46 which covers the organic ELelement, in addition to the advantage of increasing the mechanicalstrength of the film to protect the organic EL element from the externalimpact, the advantage of reliably preventing deterioration of theorganic EL element (the organic compound layer 31 in particular) byintrusion of foreign moisture and oxygen at the time of deformation ofthe substrate or even under high temperature and high humidityenvironment.

[0119] Further, because a flexible substrate 12 using a plastic materialhas higher permeability of moisture and oxygen than a glass substrate orthe like, it is necessary to prevent moisture or the like frompermeating into the substrate 12 and entering the organic EL elementregion. Thus, it is preferable to form a further protective film betweenthe substrate 12 and the element region. Here, by providing a laminatefilm having a vapor deposition inorganic film interposed between plasmapolymerized films as the first protective film 45 between the substrate12 and the element, it is possible to prevent cracking and peeling-offof the film even when the substrate is deformed and also to preventintrusion of moisture into the organic EL element region even under hightemperature and high humidity conditions. Of course, the most effectiveresults regarding both bending stress durability and moisture proofproperty can be obtained, when the above-described multi-layer laminatestructure formed by a vapor deposition inorganic film and a plasmapolymerized film is used for both the first and second protective films45 and 46.

[0120] As the plasma polymerized film 47, a plasma polymerized filmincluding any of amorphous carbon nitride, amorphous carbon, heterofive-membered ring plasma polymer such as furan and pyrrole, methacrylicacid methyl plasma polymer, acrylic organic compound plasma polymer suchas acrylonitrile plasma polymer, fluorine organic compound plasmapolymer such as tetrafluoroethylene plasma polymer, chlorine organiccompound polymer such as dichloroethylene plasma polymer, tetra ethoxysilicon plasma polymer, and silicon organic compound plasma polymer suchas hexamethyldi-silazane plasma polymer can be used. When an amorphouscarbon nitride (a-CNx:H) film is used as the plasma polymerized film 47,the film is formed by a polymerization method using a mixture of methanegas and nitrogen gas as a raw material. When furan plasma gas is used,the film is formed by a plasma polymerization method using vaporizedfuran as a raw material. When the polymer film 47 is formed using theseplasma polymerization methods, it is possible to reliably prevent damageof the organic EL element caused by heat generated at the time of filmformation because the substrate can be maintained at room temperature.

[0121] On the other hand, the vapor deposition inorganic film 48 can beformed by a nitrogen film such as silicon nitride (Si₃N₄ film), aluminumnitride, and boron nitride, an oxide film such as silicon oxide (SiO₂film), aluminum oxide (Al₂O₃ film), and titanium oxide (TiO₂ film, TiCOfilm, etc.), one of amorphous silicon and diamond like carbon (DLC), ora mixed film including one of these materials. The vapor depositionmethod includes a plasma CVD (chemical vapor deposition) method, an ALE(atomic layer epitaxial growth) method, a cat (catalyst)-CVD method, orthe like. In order to form a silicon nitride film as the vapordeposition inorganic layer 48, the film can be formed by the plasma CVDmethod using silane gas, nitrogen gas and ammonia gas as raw materials.

[0122] In the example shown in FIG. 11, the first protective film 45provided between the substrate 12 and the element region has afour-layer structure of plasma polymerized film/vapor depositioninorganic film/plasma polymerized film/vapor deposition inorganic film,sequentially formed from the substrate side. The number of laminatedlayers is, however, not limited to four, and a three-layer structure ofplasma polymerized film/vapor deposition inorganic film/plasmapolymerized film, or four or more layered structure can also be adopted.For example, with ten or more layered structure, moisture proof propertycan be enhanced. However, when the protective film includes too manylayers, the manufacturing cost rises while the protection functionremains the same, or transparency may be lowered when the film needs tobe transparent. Therefore, the laminated layers preferably number 50 orless.

[0123] In the example shown in FIG. 11, the second protective film 46which covers the organic EL element also has a four-layer structure ofplasma polymerized film/vapor deposition inorganic film/plasmapolymerized film/vapor deposition inorganic film, sequentially formedfrom the substrate side. The number of laminated layers is, however, notlimited to four, and a three-layer structure of plasma polymerizedfilm/vapor deposition inorganic film/plasma polymerized film, or four ormore layered structure can also be adopted. For example, with ten ormore layered structure, moisture proof property can be enhanced.However, when the protective film includes too many layers, themanufacturing cost rises while the protection function remains the same,or optical transparency may be lowered. Therefore, the laminated layerspreferably number 50 or less.

[0124] In order to reliably prevent occurrence of cracks or the like inthe vapor deposition inorganic film caused by bending stress and thermalstress, it is desirable to form both the first and second protectivefilms 45 and 46 in at least three-layer structure of plasma polymerizedfilm/vapor deposition inorganic film/plasma polymerized film.

[0125] Further, the following advantages can be obtained when the numberof laminated layers in the first and second protective films 45 and 46is determined such that the innermost layer with respect to the organicEL element is the vapor deposition inorganic layer 48 and the outermostlayer with respect to the organic EL element is the plasma polymerizedfilm 47 in both protective layers.

[0126] The outermost layer will first be described. In the firstprotective film 45, by forming the plasma polymerized film 47 as theoutermost layer (on the substrate side), it is possible to maintain ahigh level of adhesion between the substrate using a plastic material orthe like and the plasma polymerized film 47 including an organiccompound for a long time. This is because, when compared to the vapordeposition inorganic film, the plasma polymerized film 47 including anorganic compound has a smaller difference in the thermal stress withrespect to the plastic substrate 12 and is resistant to being peeled offthe substrate, and, because the plasma polymerized film 47 is relativelysoft and has high stress relaxation function, it is further resistant topeeling off during deformation of the substrate.

[0127] With regard to the second protective film 46, by placing theplasma polymerized film 47 as the outermost layer (on the externalside), the plasma polymerized film 47 will be able to provide highadhesion to a protective layer which will be further provided on theprotective film 46 by a coating material. This is very effective in acase where, because sufficient mechanical strength cannot be obtained bycovering the organic EL element on the opposite side of the substrateonly with the above-described second protective film 46 and the elementis likely to be damaged by an external force such as friction andimpact, it is necessary to provide a hard coating material or the likeon the second protective film 46. Namely, while many of the materialsused in the vapor deposition inorganic film have low adhesion to acoating material and an adhesive including an organic compound, theplasma polymerized film 47 including an organic compound has excellentadhesion to these coating material and adhesive. Accordingly, byproviding the plasma polymerized film 47 as the outermost layer of thesecond protective film 46, it is possible to apply a coating materialdirectly on the second protective film 46 and to adhere a film-likecoating material to the second protective film 46.

[0128] It should be noted that a coating material which can be formed onthe second protective film 46 is not particularly limited, and acrylic,fluorine, silicone, rubber or hybrid type coating materials can be used.

[0129] Further, a coating material which can be adhered onto the secondprotective film 46 includes a film-like coating film. For example, anaromatic nylon film (oriented or not-oriented), a PET film, an EVOH(ethylene-vinyl alcohol) film, a polyethylene film may be used. Inaddition, as an adhesive for bonding these films onto the secondprotective film 46, various resins including a light curing resin,thermosetting resin, epoxy resin, or the like can be used.

[0130] Next, the layer of the first and second protective films 45, 46provided on the element region side (i.e., the innermost layer) will bedescribed. Although the innermost layer may be either the plasmapolymerized film 47 or the vapor deposition inorganic film 48, in theembodiments of the present invention, the vapor deposition inorganicfilm 48 is provided as the innermost layer both in the first and secondprotective films 45 and 46.

[0131] As schematically shown in FIG. 12, in an organic EL element, anorganic compound layer 31 is formed between first and second electrodes12 and 15, and the first and second electrodes 12, 15 are in contactwith the innermost layers of the first and second protective films 45and 46, respectively.

[0132] A SiN film, which is an example of the vapor deposition inorganicfilm 48, has high absorptivity to a surface of a metal material or thelike because its raw material, silane, is chemically active. Theabsorptivity of a SiN film is higher than that of an a-CNx:H film of theplasma polymerized film 47. Because many of the materials used for thevapor deposition inorganic film 48 have such a property, when theinnermost layer of the protective film is formed by the vapor depositioninorganic film 48, the protective film can provide high adhesion to thefirst and second electrodes 12 and 15 of the organic EL element whichare made of a metal or metal oxide. Further, by covering the sidesurfaces of the organic EL element with the vapor deposition inorganicfilm 48, which has higher shielding ability against moisture or the likethan the plasma polymerized film 47, and reliably preventing intrusionof external moisture or the like into the organic compound layer fromthe element side surfaces, the organic compound layer 31 can beprotected more reliably.

[0133] The plasma polymerized film 47, when formed by an a-CNx:H filmfor example, may have dependency on the underlying layer. The plasmapolymerized film 47 which is made of such a material can be more denseand have higher shielding against moisture and oxygen, when a dense filmsuch as a SiN film is provided as the underlying layer. Accordingly, animproved function can be obtained when the vapor deposition inorganiclayer 48 is used as the innermost layer (a layer provided on the organicEL element side) at least for the second protective film 46 which coversthe organic EL element.

[0134] When both the innermost layers of both the first and secondprotective films 45, 46 are formed using the vapor deposition inorganicfilms 48, it is preferable that these vapor deposition inorganic films48 are made of the same material so as to prevent stress generation attheir interface.

[0135] For the above-described reasons, it is preferable that, in boththe first and second protective films, the layer located on the organicEL element side is the vapor deposition inorganic layer 48.

[0136] The thickness of each of the plasma polymerized film 47 and thevapor deposition inorganic film 48 in the first and second protectivefilms 45, 46 will be described. As described above, the vapor depositioninorganic film 48 is more influenced by stress and reduces its bendingstress durability or the like as the thickness of the film increases. Onthe other hand, because the vapor deposition inorganic film 48 forms alaminate structure with the plasma polymerized film 47 having excellentbending stress durability, it is not necessary to cover the step of theorganic EL element only with the vapor deposition inorganic film. It istherefore preferable that the vapor deposition inorganic film 48 has athickness of at least 0.5 μm or less so as to provide as high bendingstress durability as possible, and preferably has a smaller thickness ofapproximately 0.15 μm, for example. Here, the thickness of 0.5 μmsubstantially corresponds to the total film thickness of a normalorganic EL element and may seem to be thin. However, because the vapordeposition inorganic film 48 is formed by a vapor deposition method,even a relatively thin film can reliably cover the steps. In addition,because the vapor deposition inorganic film 48 forms a multi-layerlaminate structure with the plasma polymerized film 47, sufficientmoisture proofing property and step covering property can be achieved bythe protective film as whole, even when the vapor deposition inorganiclayer 48 is a single thin layer.

[0137] The plasma polymerized film 47, on the other hand, need not bethin because it has a high bending stress durability as described above,and it is sufficient to adjust the thickness of the plasma polymerizedfilm 47 such that the total thickness of the second protective film 46can sufficiently cover the steps of the organic EL element. For example,the plasma polymerized film 47 can have a thickness of approximately 0.5μm. Further, when the plasma polymerized films 47 are formed with thevapor deposition inorganic film 48 interposed therebetween, it isnecessary to cancel warping or the like caused by thermal stress betweenthe plasma polymerized film 47 and the inorganic film 48. It istherefore preferable that at least the plasma polymerized films 47sandwiching the inorganic layer 48 are formed by the same material tohave the same thickness.

[0138] The second protective film 46 covering the organic EL elementpreferably has a total thickness corresponding to at least approximatelythe total thickness of the organic EL element (approximately 0.5 μm inmany cases), and sufficient protection effect can be obtained when thesecond protective film 46 has at most approximately 10 μm. With thesecond protective film 46 having such a thickness range, it is possibleto sufficiently cover the steps of the organic EL element and provideresistance to moisture.

[0139] While a plastic material has been described as an example of thesubstrate 12 in the above example, the substrate 12 is not limited to aplastic substrate, and a thin glass substrate, a semiconductorsubstrate, an insulator substrate, or the like, which are easy to bend,can also be used. Even a material with substantially small deformation,such as glass, would be bent easily and be flexible, when it is formedas a very thin substrate or as a substrate formed by lamination of sucha thin glass substrate and plastic film. Therefore, when an organicelectronic element is formed on such a substrate, it is similarlypossible to obtain increased reliability and extended life of theelement by using a protective film which has a laminate structure formedby plasma polymerized films sandwiching a vapor deposition inorganicfilm as described above and which has an excellent bending stressdurability and moisture proof property. It should be noted that,although the protective film of the present invention is ideal forprotection of the organic electronic element which is formed on aflexible substrate, similar significant effects can, of course, beachieved even when, for example, the film is used for protecting anorganic electronic element formed on a glass substrate having a normalthickness with less deformation.

[0140] Further, while an organic EL element has been described as anexample of an organic electronic element, the protective film cansimilarly provide a significant effect when used for other elementsrequiring protection from moisture and oxygen, such as, for example, anorganic transistor using an organic material as a material of the activelayer, an element using liquid crystal which is an organic compound, orthe like.

EXAMPLES 1 to 7

[0141] Hereinafter, examples in which an adhesion layer of the presentinvention including amorphous carbon nitride was adopted in a laminatestructure having an organic member formed on an inorganic member, willbe described as Examples 1 and 2. In subsequent Examples 3, 4, 5, and 6,a laminate structure having an inorganic member formed on an organicmember will be described. In Example 7, a laminate structure formed by abase member which has adhesion difficulty and an adhesive will bedescribed.

Example 1

[0142] In Example 1, a glass substrate was used as an inorganic member,and an amorphous carbon nitride film having a thickness of 200 nm wasformed on the glass substrate as an adhesion layer. On this amorphouscarbon nitride film, a nylon film was attached using an ultravioletcuring resin (WORLD LOCK manufactured by Kyoritsu Kagaku, No. 8723K7C)which is an organic member. The amorphous carbon nitride film was formedby a plasma CVD method using methane gas and nitrogen gas as rawmaterials. The pressure within a film forming chamber was 200 mTorr (1Torr≈133 pa), the flow rate of methane gas was 10 sccm, the flow rate ofnitrogen gas was 5 sccm, and plasma introduction power was 20 W. Thetemperature of the glass substrate at the time of film formation was setto room temperature. A #7059 substrate from Corning (surface opticalpolished product) was used as the glass substrate.

[0143] As a comparative Example 1, on the same glass substrate as usedin Example 1, a nylon film was directly attached using the sameultraviolet curing resin.

[0144] The laminate product of Example 1 and the laminate product of theComparative Example 1 were left to stand for 1000 hours under theenvironment of 65° C. and humidity of 95% RH. As a result, noabnormalities such as film peel-off were observed in the laminateproduct of Example 1, whereas in the laminate product of the ComparativeExample 1, the glass substrate and the ultraviolet curing resin werepeeled off from each other.

Example 2

[0145] In Example 2, a glass substrate which is similar to that used inExample 1 was used as an inorganic material. On the glass substrate, anamorphous carbon nitride film having a thickness of 200 nm was formedunder the same conditions as in Example 1. Then, on this amorphouscarbon nitride film, a furan plasma polymerized film which is an organicmember was formed to have a film thickness of 2 μm using furan monomeras a raw material under the condition of the pressure of 200 mTorr,plasma introduction power of 20W, and the base member temperature at aroom temperature.

[0146] As a Comparative Example 2, on the glass substrate similar tothat used in Example 2, a furan plasma polymerized film was directlyformed under the same film formation conditions as in Example 2.

[0147] The laminate product of Example 2 and the laminate product ofComparative Example 2 were left to stand for 1000 hours under theenvironment of 65° C. and humidity of 95% RH. As a result, noabnormalities such as film peel-off were observed in the laminateproduct of Example 2, whereas in the laminate product of ComparativeExample 2, peel-off and cracks were observed for the furan film.

Example 3

[0148] In Example 3, an acrylic substrate was used as a base member. Onthis acrylic substrate, an amorphous carbon nitride film was formed onthe same conditions as those in Example 1. Then, a silicon oxide filmhaving a thickness of 500 nm was formed on the amorphous carbon nitridefilm with the SiO₂ target by an RF magnetron sputtering method usingAr/O₂ mixed gas (mixture ratio=7:3) under the conditions in which thepressure was 3 mTorr and the base member was held at a room temperature.

[0149] As a comparative Example 3, on the same acrylic substrate as inExample 3, a silicon oxide film was directly formed under the sameconditions as in Example 3.

[0150] The laminate product of Example 3 and the laminate product ofComparative Example 3 were left to stand for 1000 hours under theenvironment of 65° C. and humidity of 95% RH. As a result, noabnormalities such as film peel-off were observed in the laminateproduct of Example 3, whereas in the laminate product of ComparativeExample 3, cracks occurred in the silicon oxide film.

[0151] The above acrylic substrate can be used as a substrate for aliquid crystal display device or a plastic window base member, forexample. It is desirable that a surface of such a base member be coveredfor protection with an SiO₂ layer which functions as a hard coat layeras in Example 3. However, as is obvious from the durability test inComparative Example 3, sufficient durability of the hard coat layercannot be obtained when the silicon oxide film is directly formed on theacrylic substrate by sputtering. By forming an amorphous carbon nitridefilm between the acrylic substrate and the hard coat layer such as asilicon oxide film as in Example 3, on the contrary, it is possible toenhance adhesion of the silicon oxide film to the acrylic substrate.

Example 4

[0152] In Example 4, a poly (methyl methacrylate) substrate was used asa base member, and an amorphous carbon nitride film was formed on thissubstrate under the same conditions as in Example 1. On the amorphouscarbon nitride film, a silicon oxide film having a thickness of 500 nmwas formed under the same conditions as in Example 3.

[0153] As a comparative Example 4, a silicon oxide film was directlyformed on the same poly (methyl methacrylate) substrate as used inExample 4 under the same conditions as in Example 4.

[0154] The laminate product of Example 4 and the laminate product ofComparative Example 4 were left to stand for 1000 hours under theenvironment of 65° C. and humidity of 95% RH. As a result, noabnormalities such as film peel-off were observed in the laminateproduct of Example 4, whereas in the laminate product of ComparativeExample 4, cracks occurred in the silicon oxide film.

[0155] The above poly (methyl methacrylate) substrate has a superiortransparency and is used for a plastic lens base member, for example. Itis desirable that the durability of a hard coat layer covering thesurface of such a substrate be increased. Accordingly, by forming anamorphous carbon nitride film is formed as an adhesion layer between thepoly (methyl methacrylate) substrate and the hard coat layer such as asilicon oxide film, adhesion of the hard coat layer to the poly (methylmethacrylate) substrate is significantly increased, which results in theenhanced durability of the lens or the like.

Example 5

[0156] In Example 5, a fluorocarbon resin (more specifically,polytetrafluoroethylene) substrate was used as a base member, and anamorphous carbon nitride film was formed on this fluorocarbon resinsubstrate under the same conditions as in Example 1. On the amorphouscarbon nitride film, a silicon oxide film having a thickness of 500 nmwas formed under the same conditions as in Example 3.

[0157] As Comparative Example 5, on the fluorocarbon resin (morespecifically, polytetrafluoroethylene) substrate which is the same as inExample 5, a silicon oxide film was directly formed under the sameconditions as in Example 5.

[0158] The laminate product of Example 5 and the laminate product ofComparative Example 5 were left to stand for 1000 hours under theenvironment of 65° C. and humidity of 95% RH. As a result, noabnormalities such as film peel-off were observed in the laminateproduct of Example 5, whereas in the laminate product of ComparativeExample 5, the silicon oxide film peeled off.

[0159] Although polytetrafluoroethylene has superior chemical stabilityand is often used for a coating layer, polytetrafluoroethylene peelseasily because of low adhesion to other materials. Further, although itis desirable that a surface of polytetrafluoroethylene, which is a softmaterial, be covered with a harder material, when a silicon oxide filmwas directly formed on a polytetrafluoroethylene surface as inComparative Example 5, the silicon oxide film would be peeled offbecause of low adhesion. However, as can be recognized from the resultof Example 5, by using an amorphous carbon nitride film according to thepresent invention as an adhesion layer, adhesion between apolytetrafluoroethylene substrate and a coating member such as a siliconoxide film can be enhanced.

Example 6

[0160] In Example 6, a glass substrate which is similar to that used inExample I was used as a base member, and a color filter was formed onthis glass substrate using a CFPR resist manufactured by Tokyo OhkaKogyo Co., Ltd. On the color filter, an amorphous carbon nitride filmhaving a thickness of 200 nm was formed under the same conditions as inExample 1, and a silicon oxide film having a thickness of 500 nm isfurther formed thereon under the same conditions as in Example 3.

[0161] As a comparative Example 6, on the same glass substrate as inExample 6, a silicon oxide film is directly formed under the sameconditions as in Example 6.

[0162] The laminate product of Example 6 and the laminate product ofComparative Example 6 were left to stand for 1000 hours under theenvironment of 65° C. and humidity of 95% RH. As a result, noabnormalities such as film peel off were observed in the laminateproduct of Example 6, whereas in the laminate product of ComparativeExample 6, cracks were generated in the silicon oxide film.

[0163] A laminate structure formed by a color filter and a silicon oxidefilm is often used in a liquid crystal display device, an organicelectroluminescence device, or the like. FIG. 2A shows an example inwhich a laminate structure having an adhesion layer as described inExample 6 is applied to a liquid crystal display device.

[0164] Such a liquid crystal display device comprises a pair oftransparent substrates 112 having electrodes 114, 122 and alignmentfilms 116 covering these electrodes formed on the respective opposingsurfaces, and liquid crystal 120 which is sealed between thesesubstrates 112. In a liquid crystal display device for color display, acolor filter (CF) 130 is formed on one of the substrates (a glasssubstrate or a film substrate) 112, and on the surface of this substrate112 facing the liquid crystal, a transparent electrode 114 made of ITOor the like is formed for driving the liquid crystal between thiselectrode 114 and the electrode 122 of the other substrate 112. Here,between this transparent electrode 114 and the color filter 130, asilicon oxide (SiO₂) film 110 may be formed as an insulating film forinsulation protection of the transparent electrode 114, for example. Inthis regard, when a silicon oxide film which is an inorganic member isdirectly formed on a color filter which is an organic member, adhesionis insufficient, as in the case of Comparative Example 6. When anamorphous carbon nitride film is formed as an adhesion layer 20 betweenthe color filter 130 and the silicon oxide film 110 as shown in FIG. 2A,however, adhesion between the color filter and the silicon oxide film isincreased as can be understood from the characteristics of Example 6,and further, a protection ability to enhance shielding against intrusionof moisture, oxygen, or impurities into the liquid crystal layer fromthe color layer can be provided. It is therefore possible to enhancedurability and reliability of the device, such as resistance to hightemperatures. In some cases, a transparent electrode is directly formedon the color filter without providing a silicon oxide film. Even in sucha case, adhesion between the color filter which is an organic member andthe transparent electrode can be enhanced by providing an amorphouscarbon nitride film according to the present invention as an adhesionfilm between these layers.

[0165]FIG. 2B shows an example in which a laminate structure asdescribed in Example 6 is applied to an organic electroluminescencedevice. An organic EL device includes an element having an organic layer150 which includes an organic emissive material between electrodes 142and 152. When color display is achieved using an organic emissivematerial which emits light of a single color (for example, white),colors filters 130 of R, G, and B are provided on the light emissionside. In this case, as in the case shown in FIG. 2A, on the color filter130, which is an organic member formed on a transparent substrate 140such as a glass or film substrate, a transparent electrode 142 such asITO which forms one electrode of the organic EL element is layered via asilicon oxide film 110 or the like. (The silicon oxide film may beomitted in some cases). When an amorphous carton nitride film 20 isformed as an adhesion layer between the color filter 130 and the siliconoxide film 110 or the transparent electrode 142, adhesion between theselayers can be enhanced, and, at the same time, a protective ability forenhancing the shielding against intrusion of moisture, oxygen, orimpurities into the organic layer from the color layer can be provided,which can significantly contribute enhancement of durability andreliability of the organic EL device. In the organic EL device shown inFIG. 2B, a protective film 160 is provided so as to cover the entiredevice from above the electrode 152 which is the uppermost layer of theorganic EL element.

Example 7

[0166] In Example 7, a glass substrate which is similar to that used inExample 1 was used as a base member, and an amorphous carbon nitridefilm having a thickness of 200 nm was formed on this glass substrateunder the same conditions as in Example 1. On the other hand, anamorphous carbon nitride film was formed on a surface of a polyethylenefilm under the same conditions as in Example 1. The polyethylene filmand the glass substrate were then attached to each other in such amanner that the amorphous carbon nitride films on the respectivesurfaces of the polyethylene film and the glass substrate faced eachother and were bonded to each other using an epoxy resin (Aralditestandard manufactured by NICHIBAN CO., LTD.) applied on the amorphouscarbon nitride films.

[0167] As Comparative Example 7, an amorphous carbon film is formed on aglass substrate, and a polyethylene film is directly attached on thesubstrate using an epoxy resin.

[0168] The laminate product (adhesive product) of Example 7 and thelaminate product (adhesive product) of Comparative Example 7 were leftto stand for 1000 hours at a temperature of 65° C. and humidity of 95%RH. As a result, no abnormalities such as film peel-off were observed inthe laminate product of Example 7, whereas in the laminate product ofComparative Example 6, the polyethylene film and the epoxy resin werepeeled off from each other.

[0169] As is obvious from Comparative Example 7, the polyethylene filmhas low adhesion to the epoxy resin. By forming an amorphous carbonnitride film between the polyethylene film and the epoxy resin, adhesionbetween these layers can be reliably achieved.

Examples 8 to 12

[0170] Examples 8 to 12 and Comparative Examples 8 to 10 will bedescribed. In Examples 8 to 11, and Comparative Examples 8 and 9,organic EL elements having the same structure were used.

[0171] Referring to FIG. 5, the element portion of the organic ELelement was formed by sequentially laminating, on a glass substrate 11,a first electrode 13, a hole injection layer 32, a hole transport layer33, a hole transport layer 34, and a second electrode 15 having anelectron injection layer 14 in this order. The organic EL elements usedin Example 12 and Comparative Example 10 also have the same structureexcept that a film substrate 12 made of polyethylene terephthalate (PET)was used in place of the glass substrate.

[0172] More specifically, in Examples 8 to 12 and Comparative Examples 8to 10, the organic EL element includes, on the substrate 10 (orsubstrate 11), ITO (Indium Tin Oxide) having a thickness of 150 nm asthe first electrode 13, copper phtalocyanine (CuPc) having a thicknessof 10 nm as the hole injection layer 32, triphenylamine tetramer (TPTE)having a thickness of 50 nm as the hole transport layer 33, quinolonolaluminum complex (Alq₃) having a thickness of 60 nm as the holetransport layer 34, lithium fluoride (LiF) having a thickness of 0.5 nmas the electron injectiong layer 14, and aluminum (Al) having athickness of 100 nm as the second electrode 15, which are formed on thesubstrate 10 (or substrate 11). In Examples 8 to 11, and ComparativeExamples 8 and 9, a glass substrate on which ITO was previously formedwas used, and each layer other than ITO was formed in-situ (ultrahighvacuum process) using a vacuum evaporation method.

Example 8

[0173] In Example 8, a single layer formed by an a-CNx:H film was usedas a protective film covering the organic EL element. The crosssectional structure shown in FIG. 5 corresponds to that of the organicEL element according to Example 8. In Example 8, an a-CNx:H was formedby a plasma enhanced chemical vapor deposition method using methane gasand nitrogen gas as raw materials so as to cover the organic EL elementfrom the second electrode 15 side. During film formation, the pressurewas 200 mTorr (1 Torr≈133 pa), the flow rate of methane gas was 10 sccm,the flow rate of nitrogen gas was 5 sccm, the plasma introduction powerwas 20 W, and the temperature of the substrate was set to a roomtemperature. The a-CNx:H film was formed to have a thickness of 2 μm.

Example 9

[0174] In Example 9, as shown in FIG. 6 described above, the protectivefilm 40 covering the organic EL element has a laminate structure formedby an a-CNx:H film 41 and a SiN film 43. More specifically, the a-CNx:Hfilm 41 was first formed so as to cover the organic EL element from thesecond electrode 15 side, and the SiN film 43 was then formed thereon.The thickness of the a-CNx:H film 41 was 2 μm and was formed under theconditions similar to those in Example 8. The SiN film 43 was formed bya plasma CVD method using silane gas, ammonia gas, and nitrogen gas asraw materials. During the SiN film formation, the pressure was 400mTorr, the flow rate of silane gas was 30 sccm, the flow rate of ammoniagas was 30 sccm, the flow rate of nitrogen gas was 250 sccm, the plasmaintroduction power was 10 W, and the temperature of the substrate wasset to 100° C. The SiN film was formed to have a thickness of 0.1 μm.

Example 10

[0175] In Example 10, as shown in FIG. 7 described above, the protectivefilm 40 covering the organic EL element has a structure in which a SiNfilm 43 and an a-CNx:H film 41 were laminated in this order from theorganic EL element side. Although the order of film lamination differed,the film formation conditions and the film thicknesses are the same asthose in Example 9.

Example 11

[0176] In Example 11, as shown in FIG. 8 described above, the protectivefilm 40 covering the organic EL element has a three-layer structure ofSiN film 43/ a-CNx:H film 41/ SiN film 43 which are sequentiallyprovided from the organic EL element side. Both the SiN film coveringthe organic EL element and the SiN film which is the uppermost layer hada thickness of 1 μm and were formed under the same conditions as inExample 2. The a-CNx:H film 41 was formed to have a thickness of 2 μmunder the same conditions as in Example 8.

Example 12

[0177] In Example 12, as shown in FIG. 9, a PET film substrate 12 wasused as a substrate used for forming an organic EL element. On this filmsubstrate 12, as a protective film (buffer layer) 21, an a-CNx:H film 42having a thickness of 2 μm was formed covering the substrate and a SiNfilm 44 having a thickness of 0.1 μm was then formed to cover thea-CNx:H film 42. The film formation method was the same as that in eachof the above examples. Further, on the SiN film 44, an organic ELelement was formed as in each of the above examples. Then, a protectivefilm 40 was formed covering the organic EL element. The protective film40 was formed by sequentially laminating, from the element side, a SiNfilm 43 having a thickness of 1 μm and an a-CNx:H film 41 having athickness of 2 μm in a manner similar to Example 3 under the sameconditions as in Example 3.

Comparative Example 8

[0178] In Comparative Example 8 corresponding to the above Example 8, aSiN film which was an inorganic protective film having a thickness of 2μm was formed using a plasma CVD method as a protective film forcovering the organic EL element formed on the glass substrate. Theconditions for forming the SiN film were otherwise as described above.

Comparative Example 9

[0179] In Comparative Example 9, a polyparaxylene film which was anorganic protective film having a thickness of 2 μm was formed using aCVD method, as a protective film for covering the organic EL elementformed on the glass substrate.

Comparative Example 10

[0180] In Comparative Example 10, an a-C:H (amorphous carbon) filmhaving a thickness of 2 μm was formed as a protective film for coveringthe organic EL element formed on the glass substrate by a plasma CVDmethod using methane gas as a raw material.

[0181] Evaluation

[0182] The samples of the above examples and comparative examples thusformed were annealed in the atmosphere at 100° C. for one hour. Thesample of Example 5 in which a film substrate was used was, however,annealed at 60° C. for one hour. After annealing under the aboveconditions, a high temperature test and a high humidity test wereperformed.

[0183] In the high temperature test, each organic EL element was causedto emit light for 1000 hours under an environmental temperature of 85°C., and the changing rate in the emissive area before and after exposurewas measured. In the high humidity test, each sample was left to standunder the conditions of the temperature at 65° C. and the humidity of95% RH for 100 hours, and the changing rate in the emissive area beforeand after exposure was measured. The results are shown in Table 1. TABLE1 High temperature High humidity test (%) test (%) Example 8  89 81Example 9  95 90 Example 10 98 93 Example 11 99 or more 99 or moreExample 12 85 80 Comparative Example  0 99 or more 8 Comparative Example66 32 9 Comparative Example 82 Peeled off 10 

[0184] With all of Examples 8 to 12, over 80% of the emissive wasmaintained after both the high temperature and high humidity tests. TheComparative Examples 8 to 10, however, could only provide results inwhich the emissive area was below 50% for either the high temperature orhigh humidity test. More specifically, when only a SiN inorganic filmwas provided as a protective film as in Comparative Example 8, while theproduct showed high resistance under the high humidity conditions, thewhole region became non-emissive as a result of the high temperaturetest. On the other hand, when only an a-C:H film was adopted as inComparative Example 8, while a preferable result of 82% could beobtained under the high temperature, the protective film was peeled offas a result of the high humidity test. It can therefore be understoodthat a single layer formed by a SiN film and an single layer formed byan a-C:H film is not suitable for an in-vehicle device which requireshigh resistance to at least temperature and humidity. Further, when apolyparaxylene film was used as a protective film as in ComparativeExample 9, although the results of both the high temperature test andthe high humidity test were not bad (approximately 0%), the values of66% for the high temperature test and of 32% for the high humidity testwere both insufficient. Accordingly, the protective film in ComparativeExample 9 is also not suitable for an in-vehicle device which requireshigh resistance to temperature and humidity.

[0185] In contrast to the comparative examples, the a-CNx:H film whichis an organic member according to the present invention can provide apreferable result of 89% for the high temperature test and 81% for thehigh humidity test, even when it was used in a single layer structure asin Example 8. Further, when a two-layer structure formed by an a-CNx:Hfilm and a thin SiN film was used as in Examples 9 and 10, the enhancedfunction of the protective film was made clear. It can be understoodthat the higher effect can be achieved when these two films werelaminated in the order employed in the Example 10. In addition, in theExample 11 in which a protective film having a three-layer structure ofSiN/a-CNxH/SiN was used, a stable emissive area of 99% or more wasachieved after both the high temperature and high humidity tests, and itcan be seen that such a protective film is especially effective as aprotective film of an organic EL element for an in-vehicle use.

[0186] Further, in the element of the Example 12 using a film substrate,the emissive area of 85% after the high temperature test and theemissive area of 80% after the high humidity test were achieved. Theseresults show that it is possible to drastically increase resistance ofthe organic EL element to the high temperature and high humidity due tothe protective films 21 and 40 used in the Example 12, even when a filmsubstrate which has an inferior shielding ability with respect tomoisture and oxygen compared to a glass substrate is used.

Examples 13 to 17

[0187] Organic EL devices according to Examples 13 to 17 and organic ELdevices according to Comparative Examples 11 to 15 will next bedescribed.

[0188] In all these examples and the comparative examples, the organicEL elements formed on a substrate have the same structure. As shown inFIG. 12, each organic EL element was formed by sequentially laminating afirst electrode 13, a hole injection layer 32, a hole transport layer33, a hole transport layer 34, and a second electrode 15 having anelectron injection layer 14 in this order from the substrate 11 side.

[0189] More specifically, in Examples 13 to 17 and Comparative Examples11 to 15, the organic EL element includes ITO (Indium Tin Oxide) havinga thickness of 150 nm as the first electrode 13, copper phtalocyanine(CuPc) having a thickness of 10 nm as the hole injection layer 32,triphenylamine tetramer (TPTE) having a thickness of 50 nm as the holetransport layer 33, quinolonol aluminum complex (Alq₃) having athickness of 60 nm as the hole transport layer 34, lithium fluoride(Lif) having a thickness of 0.5 nm as the electron injection layer 14,and aluminum (Al) having a thickness of 100 nm as the second electrode15, which are sequentially formed from the substrate 11 side. The layersother than ITO were sequentially formed (in-situ) using a vacuumevaporation method.

[0190] Further, in each of the examples and the comparative examples, afilm substrate 12 made of polyethylene terephthalate (PET) was used as aflexible substrate.

Example 13

[0191] In the Example 13, an organic EL device having a laminatestructure as shown in FIG. 11 was formed on a PET film substrate 12.More specifically, from the substrate side, “a PET film substrate 12”,“a plasma polymerized film 47/a vapor deposition inorganic film 48/ aplasma polymerized film 47/a vapor deposition inorganic film 48”, “anorganic EL element”, “a vapor deposition inorganic film 48/a plasmapolymerized film 47/a vapor deposition inorganic film 48”, and “a plasmapolymerized film 47” were sequentially formed.

[0192] For each plasma polymerized film 47, an amorphous carbon nitride(a-CNx:H) film having a thickness of 500 nm was used. Further, for eachvapor deposition inorganic film 48, a silicon nitride film having athickness of 150 nm was used.

[0193] The amorphous carbon nitride film was formed by a plasmapolymerization method using a mixed gas of methane gas and nitrogen gas(a mixture ratio=2:1) as a raw material. During the film formation, thepressure was 200 mTorr (1 Torr≈133 pa), the plasma introduction powerwas 20 W, and the temperature of the substrate was set to a roomtemperature.

[0194] The silicon nitride film was formed by a plasma CVD method usinga mixed gas of SiH₄ gas, NH₃ gas, and N₂ gas (a mixture ratio=3:3:25) asraw materials. During the film formation, the pressure was 400 mTorr (1Torr≈133 pa), the plasma introduction power was 10 W, and thetemperature of the substrate was 100° C.

Example 14

[0195] The device of Example 14 has the same element structure as in theabove Example 13 except that in Example 14, in place of the amorphouscarbon nitride film of Example 14, a furan plasma polymerized filmhaving a thickness of 500 nm was used as the plasma polymerized film 47.The furan plasma polymerized film was formed by a plasma polymerizationmethod using vaporized furan as a raw material under the conditions inwhich the pressure was 200 mTorr (1 Torr≈133 pa), the plasmaintroduction power was 20 W, and the temperature of the substrate wasset to a room temperature.

Example 15

[0196] In the device of the Example 15, from the substrate side, “a PETfilm substrate”, “a plasma polymerized film/a vapor deposition inorganicfilm/a plasma polymerized film/a vapor deposition inorganic film/aplasma polymerized film/a vapor deposition inorganic film”, “an organicEL element”, “a vapor deposition inorganic film/a plasma polymerizedfilm/a vapor deposition inorganic film/a plasma polymerized film/a vapordeposition inorganic film/a plasma polymerized film” were sequentiallyformed. The device of the Example 15 differs from the device of theExample 13 in that while in the Example 13, the number of layers formingthe first protective film 45 provided between the substrate and theorganic EL element and the number of layers forming the secondprotective film 46 covering the organic EL element region are both 4,the number of these layers in the Example 15 are both 6. The devices ofExamples 13 and 15 are the same in other respects. Namely, as eachplasma polymerized films 47, an amorphous carbon nitride (a-CNx:H) filmhaving a thickness of 500 nm which was formed by a plasma polymerizationmethod was used. Further, as each vapor deposition inorganic film 48, asilicon nitride film having a thickness of 150 nm which was formed by aplasma CVD method was used.

Comparative Example 11

[0197] In Comparative Example 11, in a device having a laminatestructure in which films are layered in the same order as in the Example13, the thickness of the vapor deposition inorganic film 48 usingsilicon nitride was set to 1 μm contrary to the thickness of 0.15 μm inthe Example 13. The device of Comparative Example 11 is the same as thedevice of the Example 13 in other respects.

Comparative Example 12

[0198] In Comparative Example 12, from the substrate side, “a PET filmsubstrate”, “a plasma polymerized film/a vapor deposition inorganicfilm” an organic EL element” a vapor deposition inorganic film/a plasmapolymerized film” were sequentially formed. For each plasma polymerizedfilm, an amorphous carbon nitride (a-CNx:H) film having a thickness of500 nm which was formed by a plasma polymerization method was used.Further, for each vapor deposition inorganic film, a silicon nitridefilm having a thickness of 150 nm which was formed by a plasma CVDmethod was used.

[0199] The device in Comparative Example 12 differs from the devices ofExamples 13 to 15 in that in Comparative Example 12, a sandwichstructure including a vapor deposition inorganic film between plasmapolymerized films is not used either in the first protective filmprovided between the substrate and the element or in the secondprotective film covering the element.

Comparative Example 13

[0200] In Comparative Example 13, from the substrate side, “a PET filmsubstrate”, “a vapor deposition inorganic film/a plasma polymerizedfilm”, “an organic EL element”, “a plasma polymerized film/a vapordeposition inorganic film” were sequentially formed.

[0201] The device in Comparative Example 13 differs from the devices ofExamples 13 to 15 in that in Comparative Example 13, a sandwichstructure including a vapor deposition inorganic film between plasmapolymerized films is not used either in the first protective filmprovided between the substrate and the element or in the secondprotective film covering the element, and in that the inorganic layersare formed as the outermost layers with respect to the organic ELelement.

Evaluation of the Examples 13 to 15 and Comparative Examples 11 to 13

[0202] Each organic EL device in the examples 13 to 15 and inComparative examples 11 to 13 was evaluated concerning the bendingstress durability and the high temperature resistance. For evaluation ofthe bending stress durability, in each element of Examples 13 to 15 andComparative Examples 11 to 13, the substrate was bent until it had aradius of curvature of 8 mm while the element was caused to emit light,and a change of the state at that time was evaluated. Further, theelement was continuously caused to emit light while the radius ofcurvature of 8 mm was maintained, and a change of moisture proofproperty was evaluated.

[0203] For evaluation of high temperature resistance, the element wascaused to emit light at 85° C. without bending the substrate and achange in the moisture proof property of the element was evaluated.

[0204] In the device of Comparative Example 11, cracks were generated inthe first and second protective films when the radius of curvature ofthe substrate reached 15 mm, and the moisture proof property waslowered.

[0205] In the devices of Comparative Examples 12 and 13, although nocracks were generated when the radius of curvature reached 8 mm, as aresult of continuously causing the element to emit light while keepingthe radius of curvature of 8 mm, the non-emissive area (dark spots)increased within the original emissive area of the organic EL elementafter elapse of 300 hours, and deterioration of moisture proof propertywas observed.

[0206] In each device of Examples 13 to 15, on the other hand, crackswere not generated when the radius of curvature reached 8 mm, and as aresult of continuously causing the element to emit light for 1000 hourswhile keeping the radius of curvature of 8 mm, neither the increase ofdark spots or the deterioration of moisture proof property was observed.In addition, in the element of Examples 13 to 15, the evaluation of thehigh temperature resistance also showed no deterioration of moistureproof property for 1000 hours.

[0207] From the above evaluation results, the following was found.First, when the thickness of the vapor deposition inorganic film islarge as in Comparative Example 11, the bending stress durability cannotbe obtained and sufficient moisture proof property cannot be maintained.Therefore, a protective film having such a thick inorganic film isinappropriate when an element is formed on a flexible substrate.

[0208] Further, as can be understood from the evaluation results ofComparative Examples 12 and 13 and of Examples 13 to 15, when a laminatestructure formed by three or more layers in which a vapor depositioninorganic film is sandwiched between plasma polymerized films is used ina protective film, it is possible to reliably protect an organicelectronic element formed on a flexible substrate for a long time.Therefore, when a protective film has such a sandwich structureincluding a vapor deposition inorganic film sandwiched between plasmapolymerized films and the vapor deposition inorganic film is formed at asmall thickness, an organic electronic device having an excellent hightemperature resistance and also high bending resistance can begenerated, and an in-vehicle flexible organic electronic device whichcan resist a severe environment can be realized, for example.

Example 16

[0209] In the Example 16, in a device having the same structure as inthe Example 13, an acrylic hard coating member having a thickness of 5μm was further provided on the second protective film 46.

Comparative Example 14

[0210] In Comparative Example 14, the uppermost layer of the secondprotective film 46 of the Example 16 was formed by a vapor depositioninorganic film, not by a plasma polymerized film. More specifically,from the substrate side, “a PET film substrate”, “a plasma polymerizedfilm/a vapor deposition inorganic film/a plasma polymerized film/a vapordeposition inorganic film”, “an organic EL element”, “a vapor depositioninorganic film/a plasma polymerized film/a vapor deposition inorganicfilm/a plasma polymerized film/a vapor deposition inorganic film” weresequentially formed. Then, on the vapor deposition inorganic film whichis the uppermost layer, an acrylic hard coating member having athickness of 5 μm which is the same as that in Example 4 was provided.

Example 17

[0211] In the Example 17, in a device having the same structure as inthe Example 16, a drawn aromatic nylon film having a thickness of 15 μm,not an acrylic hard coating member, was attached to the secondprotective film 46 using a light curing resin. The device of the Example17 has the same structure as in the Example 16 in other respects.

Comparative Example 15

[0212] In Comparative Example 15, the uppermost layer of the secondprotective film 46 in the device having the same structure as in theExample 17 was formed by a vapor deposition inorganic film, not by aplasma polymerized film. More specifically, from the substrate side, “aPET film substrate”, “a plasma polymerized film/a vapor depositioninorganic film/a plasma polymerized film/a vapor deposition inorganicfilm”, “an organic EL element”, “a vapor deposition inorganic film/aplasma polymerized film/a vapor deposition inorganic film/a plasmapolymerized film/a vapor deposition inorganic film” were sequentiallyformed. Then, a drawn aromatic nylon film having a thickness of 15 μmwas attached to the vapor deposition inorganic film which is theuppermost layer, using a light curing resin, as in the Example 5.

Evaluation of Examples 16 and 17 and Comparative Examples 14 and 15

[0213] The devices of Examples 16 and 17 and the devices of ComparativeExamples 14 and 15 were left to stand on the conditions of thetemperature at 65° C. and the humidity of 95% RH for 300 hours. As aresult, no abnormality in the element, the protective film, or the hardcoating member was found in the devices of Examples 16 and 17. In thedevices of Comparative Examples 14 and 15, however, abnormality such aspeel off between the coating member and the second protective film wasobserved. From the above result, it is to be understood that it ispreferable that, especially when a protective coating member is furtherprovided on the second protective film, the uppermost layer of thesecond protective film is formed by a plasma polymerized film having ahigh affinity to such a coating member.

Industrial Applicability

[0214] The present invention can be used as an adhesion layer or aprotective film for an organic and inorganic member, which is applicableto both an organic member and an inorganic member.

1-43. (Cancelled).
 44. An organic/inorganic laminate product having anorganic member formed on an inorganic member or having an inorganicmember formed on an organic member, comprising: an adhesion layerprovided at an interface between the inorganic member and the organicmember, wherein the adhesion layer comprises amorphous carbon nitride.45. A laminate product according to claim 44, wherein the adhesion layercomprising amorphous carbon nitride is formed by a plasma enhancedchemical vapor deposition method using, as a raw material, gascomprising one or more of alkane, alkene, and alkyne, and gas comprisingnitrogen and ammonia.
 46. A laminate product according to claim 44,wherein the organic member comprises one or more of a single layer ormulti-layer thin film of an organic compound, a resin, and an adhesive.47. A laminate product according to claim 44, wherein the inorganicmember is one or more of oxide, nitride, a metal, and a semiconductor.48. A laminate product having an adhesive and a base member at least asurface of which has difficulty to adhere to the adhesive, the laminateproduct comprising: an adhesion layer between the adhesive and the basemember, wherein the adhesion layer comprises amorphous carbon nitride.49. A laminate product according to claim 48, wherein the adhesion layercomprising amorphous carbon nitride is formed by a plasma enhancedchemical vapor deposition method using, as a raw material, gascomprising one or more of alkane, alkene, and alkyne, and gas comprisingnitrogen and ammonia.
 50. A laminate product formed by either one of orboth an inorganic member and an organic member, wherein an adhesionlayer is provided between inorganic members or between organic members,or between the inorganic member and the organic member, and the adhesionlayer comprises amorphous carbon nitride.
 51. An organic electronicdevice comprising, on a base member; an organic electronic elementcomprising at least an electrode and an organic compound layer, and oneof or both a protective film which is formed covering the organicelectronic element and a protective film which is formed between theorganic electronic element and the base member, wherein the protectivefilm comprises amorphous carbon nitride.
 52. An organic electronicdevice according to claim 51, wherein, the film comprising amorphouscarbon nitride is formed by a plasma enhanced chemical vapor depositionmethod using, as a raw material, gas comprising one or more of alkane,alkene, and alkyne, and gas comprising nitrogen and ammonia.
 53. Anorganic electronic device according to claim 51, wherein the protectivefilm is a single film made of the amorphous carbon nitride or a laminatefilm formed by the amorphous carbon nitride and an inorganic film. 54.An organic electronic device according to claim 53, wherein, the filmcomprising amorphous carbon nitride is formed by a plasma enhancedchemical vapor deposition method using, as a raw material, gascomprising one or more of alkane, alkene, and alkyne, and gas comprisingnitrogen and ammonia.
 55. An organic electronic device according toclaim 53, wherein the inorganic film comprises one or more of a nitridefilm, an oxide film, and a silicon film.
 56. An organic electronicdevice according to claim 51, wherein the inorganic film is one or moreof a silicon nitride film, a boron nitride film, an aluminum nitridefilm, a silicon oxide film, an aluminum oxide film, a titanium oxidefilm, and an amorphous silicon film.
 57. An organic electronic deviceaccording to claim 51, wherein the organic electronic element comprisesan organic transistor or a liquid crystal element.
 58. An apparatus formanufacturing an organic electroluminescence element comprising anelement region having at least one organic compound layer betweenelectrodes and a protective film covering at least the element region,the protective film having a laminate structure formed by an amorphouscarbon nitride film and an inorganic film and covering the elementregion, the apparatus comprising: an element film forming chamber forforming each layer which constitutes the element region, a protectivefilm forming chamber for forming the amorphous carbon nitride film, andan inorganic film forming chamber for forming the inorganic film,wherein at least each protective film forming chamber for forming theamorphous carbon nitride film or the inorganic film which is previouslyformed covering the element region and the element film forming chamberare connected directly or via a transportation vacuum chamber.
 59. Anorganic electronic device comprising, on a base member; an organicelectronic element comprising at least an electrode and an organiccompound layer, and either one of or both a protective film formedcovering the organic electronic element and a protective film formedbetween the organic electronic element and the base member, wherein theprotective film comprises a lamination film in which a vapor depositioninorganic film and a plasma polymer film which is formed using amaterial comprising at least one type of an organic compound, arealternately layered, and the vapor deposition inorganic film issandwiched by the plasma polymer films.
 60. An organic electronic deviceaccording to claim 59, wherein the base member is made of a flexiblematerial.
 61. An organic electronic device according to claim 59,wherein the number of layers laminated in the lamination film is 50 orless, the total thickness of the lamination film is equal to or greaterthan the total thickness of the organic electronic element and is 10 μmor less, and the vapor deposition inorganic film in the lamination filmhas a thickness of 0.5 μm or less per layer.
 62. An organic electronicdevice according to claim 59, wherein the organic electronic element isa liquid crystal element, an organic electroluminescence element, or anelement comprising an organic transistor.
 63. An organic electronicdevice according to claim 59, wherein the plasma polymer film comprisesone or more of amorphous carbon nitride, hetero five-membered ringorganic compound polymer, fluorine organic compound polymer, chlorineorganic compound polymer, acrylic organic compound polymer, and siliconorganic compound polymer, and the vapor deposition inorganic filmcomprises one or more silicon nitride, boron nitride, aluminum nitride,silicon oxide, aluminum oxide, titanium oxide, and amorphous silicon.